摘要:

JOURNAL OF THE CRIEJIICAL SOCIETY. C0NTAI N IN0 THE PAPERS READ BEFORE TIIE SOCIETY AND ABSTRACTS OF CHEXICAL PAPERS PUBLISHED IN OTHER JOUEtNdLS. a~rnmittes~f @ublicrtlair I?. A. ABEL,P.R.S. w. MARCET x.D. F.R.S. E. ATKISSOS,Ph.D. N. SrOPY-JIASKELYNE F.R.S. F.C.S. E. J UILLS D.Sc. C. L. BLOXAU Ph.D. F.R.R. H. DEBUS Fh.D. F.R.S. HVGOX~LJ~ER G. C FOSTER B.A. F.R.S. W. ODLING,KB F.R.S. M.D. W. H. PERKIN, MICHAELFOSTER F.R,S. D.C.L. F.R.S. H €3. ROSCOE, E. FRANKLAND Ph.D. F.R.S. Ph,D. F.R.S. W. J. EUSSELL, J. H. GILBERT Ph.D. Ph.D. F.R.S. A. VOELCKER, J. E. GLADSTONE Ph.D. F.R.S. A. VEENON M.A. F.R.S. A. W.WiLLIatsoN PG.D. F.R.S. HARCOURT 6;bifar HENRYWATTS,B.A. F.R.S. D.Sc. WILLIAXVALENTIN. WALTERFLIGHT GILL. ROBEKr ~~ARISGIOS. 0.EAUGHTOX CHARLES WATTS,D.Sc. GEAHAJI,D.Sc. JOHN EIDY WImuJf s, C.E. GROVES. REV.STEP NEW SERIES Vol. IX. (Entire Series Vol. xxiv,) LONDON VAN TOORST 1 PATERNOSTER ROW. 1871 LONDON ! HAWISON AND aorps PRINTERS IN ORDINARY TO IIER NAJESTP GT MARTIN’U LANIC

ISSN:0368-1769    

DOI:10.1039/JS87124FP001

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

PERKIN ON SOME DERIVATIVES OF ANTHRACENE. 13 11.-On some Derivatives of Antlwacene. By W. H. PERKIN,F.R.S. INthe “Chemical News ” of the 22nd July last I published a short note upon some new derivatives of anthracene and re- ferred more particularly to the products resulting from the action of atllphuric acid upon dichlor- and dibromanthracene I now beg leave to lay before the Society a more detailed ac-count of my experiments in this direction with the addition of* a few other observations relating to the history of anthracene. PERKIN ON SOME DERIVATIVES OF ANTHRACENE. DICHLORANTHRACENE. I have found it convenient to prepare this substance by passing chlorine gas over benzole holding about one-fifth its weight of purified commercial anthracene in suspension until the mixture becomes a crystalline pasty mass.The product is then thrown on a linen filter drained and well washed with cold benzole. It is then dried and further purified first by distillation and then by two or three crystallisations from benzole. Thus obtained it presents itself as golden-yellotl coloured needles. Analysis of this product gave the following numbers :-I. 03151of substance gave -3624 of AgC1. 11. ,6258 of substance gave -7333 of AgC1. 111. *3607of substance gave *8974 of CO and *I073of H20. IV. 03143of substance gave -1833 of CO and 00957 of H20. These numbers agree with the formula- as the following comparisons show :-Theory. Experiment. / A \ -I. 11. 111. IV. C,,... 168 68.02 -67.85 6'7.97 H .... 8 3.24 -3-30 3-38 GI,. .. . 71 28-74 28.45 28.95 -7 7-247 100*00 It will be observed that theRe results perfectly agree with those of Graebe and Liebermann." Dichloranthracene when gently heated sublimes in beautiful needles which may be obtained of considerable size. It is fluorescent in the solid state as well as when in solution. * Ann. Chem. Pharm. Supp. pii 259 (1870). PERKIN ON SOME DERIVATIVES OF ANTHRACENE. When a boiling solution of dichloranthracene in benzole is added to a similar solution of picric acid the mixture assumes a dark orange-red colour and on cooling becomes filled with small bright red needles. These consist of a compound of dichloranthracene and picric acid. A determination of the di-chloranthracene in this body gave numbers closely approxi- mating to those required by the formula- DIBROMANTHRACENE.The product used in my experiments was prepared by Graebe's process*. It was however purified fist by distillation and then by crystallisation from Fenzole. Thus obtained it is of a golden-yellow colour. It gave on analysis the following numbers :-a3205 of substance gave *5864 of CO, and -0729 of H,O. These numbers closely agree with those required by the formula-'14=BBr29 as the following comparisons will show :-Theory. Experiment. C, ... . 168 Br .a * . 160 H ...... 8 - 50.00 47.62 2.38 49.9 -2-52 336 100*00 Like dichloranthracene this body produces a beautiful red compound with pic& acid.Action of Sulphuric A cid on Dichloranthracene. Dichloranthracene when submitted to the action of fuming sulphuric add dissolves forming a bright green solution and is at the aame time converted into a sulpho-acid. To prepare this acid one part of dichloranthracene is added * Ann. Ch. Phttrm Suppl. vii (1870). PERKIN ON SOME DERIVATIVES OF ANTHRACENE. to about five parts of fuming sulphuric acid and the mixture heated for a short time on the water-bath. It is then gradually poured into several times its bulk of water and treated with baric carbonate until all the sulphuric acid is neutralized. The acid solution when filtered off from the baiic sulphate is evaporated to a small bulk. When sufficiently concentrated it becomes on cooliiTg a slimy mass of minute orange-yellow coloured crystals which may be drained on a porous tile.This acid has not been analysed but from the composition of its salts evidently possesses the forrnula- I therefore propose €0 call it-Disul33hodaehloi.antliracenic Acid.-It is easily soluble in water from which it is pre-cipitated upon the addition of a little concentrated sulphuric or hydrochloric acid. It possesses a strongly acid taste and character. The dilute solutions of this acid and its salts are remarkably fluorescent but not so strongly as an alkaline srolution of pure 2Esculine. The colour of the fluorescence is blue. Xodic Di~u~ho~~c~lomnthracenale.-This salt can be obtained by neutralizing the acid with sodic carbonate or from tho calcic or crude baric salt by double decomposition.To ob-tain it from the latter the product of the action of sulphuric acid on dichloraiithracene is entirely neutralized with baric . carbonate. Sodic sulphale is then added ,in > the proportion of about five parts of dry salt to every ten parts of dichloran-thracene employed and the mixture well boiled; it is theu atered and the filtrate concentrated. On standing for some &me the new sodic salt separates iii small orange-red crystals. These are well pressed between bibulous paper and pmified by one or two crystallisations; dried at 150" C. they gave the following numbers on analysis :-I. *2254grm. of substance gave -0693 , Na,SO,. 11. -3449 , of substance gave *4694 , CO, and *0559 , H,O.PERKIN ON SOXE DERIVATIVES OF ANTHRACENE; These numbers give perceptages agreeing with those re-quired by the formula- c14H(jc19 {:::$ a8 the following comparisons will show :-Theory. Experiment. ’I. /-.11. -I C, ...... 168 37-25 37.11 H6 ...... 6 1-33 -1.80 C1,...... 71 15.74 Na,.. .... 46 10.20 S ..... 64 14-19 0 ...... -96 21-29 451 100*00 This salt dissoll-es easily in water forming an orange coloured solution. Bark Disu~hodich2oranthracenat~.-This salt is best obtained in the pure state by the addition of baric chloride to a solution of the pure sodic salt. It is then thrown down as a bright canary-yellow coloured precipitate nearly insoluble in water. The analysis of this salt gsve the following numbers :-I *2023grm.of substance gave *0859 , BaSO,. 11. -0845 , of substance gave ~0360 , BaSO,. 111. *1534 , of substance gave *0658 , BaSO,. IV. -4179 , of substance gave *4637 , CO, and 00560 , H,O. V. -4117 , of substance gave -4549 , CO,,and 00571 , H,O. VI. 03059 , of rjubstance gave ,3438 , CO, and 00448 ) H,O. VII. *5936 , of substance gave *6767 , CO, and 4878 , H,O. VOL XXIV. 0 18 PERKIN ON SOME DERIVATrCTES OF ANTHRACENE. These give percentages agreeing tolerably well with the formula-C14H6C1,Bav{:$ The following is a comparison of the theoretical and experi- mental numbers :-Theory. Experiment. F h 7 -I. 11 111. IT. v. VI. VII. CI~.... 168 30.99 --30.26 30.13 30.65 31.09 Hs....6 1-11 --1.48 1-54 1.62 164 Ba.... 137 25.28 24.96 25.05 25.22 --Clz.,.. 71 13-10 ----5 .... 64 11.81 ----06 .... 96 17.71 --542 10000 If to a hot solution of sodic disulphodichloranthracenate strongly acidified with hydrochloric acid baric chloride be added no change at first is observed but on standing a short time the above baric salt senarates as an orange-coloured I crystalline precipitate. The following numbers were obtained on analyzing a specimen prepared in this manner :-01723 of substance gave *0742of BaSO = 25.32 per cent. of barium. Xtrontic Disulphodichloratithvacenate.-On adding a solution of strontic chloride to a solution of sodic disulphodichloranthrtz- cenate no apparent change takes place; but if the solution be evaporated the new strontic salt separates in yellow crusts difficultly soluble in water.A specimen gave the following numbers on analysis :-03146of substance gave -1136 of SrSO = 17.21 per cent. of strontium. The formula Cl,H6C1,Sr”{ “3 so3 requires 17-77 per cent. Calcic ~isulphoclichlorantliracenate.-This salt may be ob-tained by neutralizing the product of the action of sulphuric acid on dichloranthracene with calcic carbonate filtering PERKIN ON SOME DERIVATIVES OF ANTHRACENE. off the calcic sulphate and evaporating the filtrate to dry-ness. The residue is extracted with water filtered and again evaporated. This salt is of a yellow colour and easily soluble in water. It is useful for the preparajion of the sodic salt by double decomposition with calcic carbonate.Action of Su&7~uricAcid upon Dibi3omanthracene. Dibromaiithracene dissolves in fuming sulphuric acid forming a sulpho-acid. This has not however been prepared in a pure state but from the examination of its salts it evidently possesses the formula- and may therefore be called disu&?Lodi6ro.rrianthracenic acid. It is crystalline and its dilute solutions are fluorescent as also are its salts but not nearly to the same extent as those of the cor- responding dichloro-acid. Sodic Disul&hodibromant?iracenate.-To obtain this salt one part of dibromanthracene is dissolved in the cold in about six or seven parts of fuming sulphuric acid and the mixture allowed to stand for an hour or two.It is then gradually added to several times its bulk of cold water well stirred and neutralized with baric carbonate. Sodic sulphate is then added in the proportion of about five parts of dry salt to every twelve parts of dibromanthracene employed and after boiling the resulting sodic salt is filtered off from the baric sulphate concentrated by evaporation over the water-bath and set aside to crystallise. It is then well drained and pressed from the mother-liquor and purified by two or three crystallisatioiis from water. Thus obtained it is of a yellow colour and crystallises in microscopic needles. It is easily soluble in water. It gave on analysis the following numbers :-I. 04676of substance gave- -1256 of Na,SO = 8-70p.c. sodium.11. -4809 of substance gave- *1311of Na,SO = 8-85p.c. sodium. 02 PERKIN ON SOME DERIVATIVES OF ANTHRACENE. The formula C,,H6Br2(1:$: requires 8-52 per cent. of sodium. Ban’c Disdphodibromnt h?*acenate.-This salt may be ob-tained in precisely the same manner as the corresponding disulphodichloranthracenate. It is obtained as a pale yellow precipitate. It gave on analysis the following result :-*5565of substance gave-*2026of BaSO = 21.41 p.c. barium The formula Cl,H6Br2Ba”{ ;$ requires 21-71 per cent. of barium. This salt is remarkable for its insolubility. If a boiling solu-tion of the sodic salt be strongly acidified with hydrochloric acid and bark chloride added the mixture which is for a few seconds perfectly clear becomes rapidly turbid with the formation of this salt which cannot be re-dissolved even by vigorous boiling notwithstanding the excess of hydrochloric acid present.Oxidation of Disull,hodicJdo~o-and DisubJLodibromanthracenic Acid.-These sulpho-acids when subjected to the influence of oxidizing agents rapidly decompose exchanging their chlorine or bromine for oxygen and are thus converted into disulphan-thraquinonic acid. Disulphodichloranthracenic Disulphanthraquinonic acid. acid. Ci*H6Br!2 { HSO + 0 = C,,R,(O,)” {E:: + BrBr Disulphodibromanthracenic Disulphanthraquinonic acid. acid. An analogous result is also obtained by heatjng them with concentrated sulphuric acid the following regctions taking place :- PERKIN ON SOME DERIVATIVES OF ANTHRACENE.21 A quantity of disulphanthraquinonic acid prepared by heating disulphodiclzloranthracenic acid with concentrated sulphuric acid was made into the baric salt,* and analysed. The fol-lowing results were obtained :-I. =2273of substance gave- -1040 of BaSO = 26.90 p.c. barium. 11. -3093 of substance gave- -1415 of BaSO = 26.89 p.c. barium. The formula C,,H60,Ba"2SO requires 27.23 p.c. Graebe and Liebermann have shown that dichlor-or dibrom-anthracene when oxidized also exchange their chlorine or bromine for oxygen yielding anthraquinone.? Whilst making the foregoing experiments I have often been struck with the remarkable fluorescence of many of the anthra- cene products anthracene itself when pure and in large crystals being one of the most beautifully fluorescent solid bodies I know of though curiously its solutions are comparatively poor in this respect.$ As this hydrocarbon aiid also its chlorine deri-vative which is fluorescent both in the solid state and in solu-X I may here remark that the baric disulphanthraquinonate although more soluble than the baric salts of the sulpho-acids obtained from dichlor or dibroman-thracene is Like them precipitated from hot solution in the preseuce of an excess of hydrochloric acid if the solution be not too dilute j a specimen prepared in this manner gave the following results upon analysis :--2135 grm.of substance gave -0981 BaS04 = 27.01 per cent. j theory 27.23. .t. When endeavouring to obtain some highly chlorinated anthracene derivatives some time since I came across a rather unexpected instance of this kind.A quantity of dichloranthracene was suspended in glacial acetic acid and chlorine passed through the mixture. On allowing this to stand a large quantity of a white product was obtained which when crystallised from benzole was analysed and gave of carbon 80.65 per cent. and of hydrogen 414 per cent. It was in fact anthraquinone which requires of carbon 80.77 and of hydrogen 3.85 and had been formed owing to the presence of a small quantity of water in the glacial acetic acid thus :-$ The anthracene used in these experiments was chemically pure and gave the following numbers on analysis :-I. 11. Theory. Carbon .......... .. 94-31 94.37 94.38 Bydrogen .,.,.,.. . 5 -68 5 98 5 -62 PERKIN ON SOME DERIVATIVES OF ANTHRACENE. tion are volatile it appeared to me interesting to examine them in the state of vapour. So far as I have gone however my experiments seem to show that the vapour of anthracene or dichloraiithracene is not fluorescent and moreover a ray of light sent through alength of about 4inches of the vaponr of either body still retained its power of rendering fluorescent solutions luminous. On sealing up anthracene in a long vacuum tube with platinum poles and allowing the discharge from an induction coil to pass through the tube nothing particular is observed except the beautiful fluorescence of the crystals of anthracene. On exa- mination with the spectroscope the light showed carbon and nitrogen lines the latter arising from the presence of a little air in the tube.Upon heating the tube however somewhat strongly so as to volatilise the hydrocarbon the ordinary colour of the discharge changed to a magnificent deep azure blue and what is remarkable is that this blue light when examined with the spectroscope is perfectly continuous and consists of blue with a little green. Dichloranthracene when treated in a similar manner g'ives an analogous result but suffers a good deal of decomposition aiithracene changing but little. These curious results do not appear to be due to the fluorescent character of the substances employed as naphthalene produces a similar effect the blue light though not so intense being coiitinuous.It must be observed however that this hydrocarbon undergoes considerable change becoming brown and oily. Anthraquinone heated in a vacuum tube in the same way gives a greenish blue light showing faint carbon bands. On exposing a solution of disulpho-dichloranthracenic acid to the light of one of the recent displays of the aurora borealis it was very strongly illuminated as might be expected moon-light on the other hand had no perceptible effect either upon it or an alkaline solution of esculin.

ISSN:0368-1769    

DOI:10.1039/JS8712400013

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

23 III.-Researcl~es on Vanadium. Part 111. By HENRY E. ROSCOE,B.A. Ph.D. F.R.S. (Abstracted from the Philosophical Transactions 1870 p. 317.) I. &TALL10 VANADIUM. INthe second part of my 6‘ Researches on Vanadium,”* I stated that metallic vanadium absorbs hydrogen. This conclusion has been fully borne out by subsequent experiment ; and it appears that the amount of absorbed or combined hydrogen taken up by the metal varies according to the state of division &st of the chloride (VC1,) from which the metal is prepared and secondly and especially of the metallic powder itself. When the metal containing absorbed hydrogen is exposed to dry air it slowly takes up oxygen water being formed and the vanadium undergoing oxidation to a substance which resembles the metal in its appearance but possesses a darker grey colour and has a less brilliant metallic lustre than vanadium itself.At this point the oxidation stops although in most air it proceeds still hrther. Thus a portion of pure dichloride was reduced in hydrogen; of the reduced substance free from chlorine 0.2666 grm. yielded on complete oxidation 0.4441 of V,O, corresponding to a percentage of 93.6 of pure metal. On expo-sure to the air for some days this substance absorbed oxygen losing its brilliant metallic lustre; and when it was burnt in a current of dry oxygen water was given off thus :-(1) 0-4232 grm. gave 030502 grm. of water and 0.6615 gin. ~2% (2) 0.2695 3 9 0.0315 0.414 grm. 3 99 V,% or (1) gives 87.8 p.c.vanadium; 1.3 p.c. hydrogen; 10.9 p.c oxygen. (2) gives 86.7 p.c. vanadium ; 1.3 p.c. hydrogen ; 12.0 p.c. oxygen. f Phil. Trans. 1869 p. 691; Chem. SOC. J. [2] vie 344. ROSCOE'S RESEARCHES ON VANADIUM. The difficulty of obtaining metallic vanadium perfectly free from admixture of oxide mas again rendered evident. Pure tetrachloride was prepared in quantity and from this the dichloride was made. On heating this dichloride to whiteness for forty-eight hours a substance was obtained which gained on oxidation 70.7 per cent. and therefore still contained a slight admixture of oxide. Tho reducing action of sodium on the solid chlorides was next examined ; in this case the reduction takes place rapidly but quietly in an atmosphere of hydrogen at a red heat and may be best conducted in strong iron tubes proved air-tight under hydraulic pressure of 200 lbs.on the square inch. Explosions occur when the tetrachloride is heated with sodium. The substance thus obtained by the action of sodium was found on lixiviation to be free from chlorine and on washing it mas found to separate into two parts-(1) a light and finely divided black powder (trioxide) soluble in hydrochloric acid which remains in suspension ; and (2) a heavier grey powder (insoluble in hydrochloric acid) which is deposited and which by repeated washing may be entirely fi-eed from the lighter trioxide. This bright grey powder con- sists of metallic vanadium mixed with more or less oxide. If the finely divided metallic powder after drying in wacuo be reduced at a low red heat in a current of pure hydrogen it takes fire spontaneously when cold on exposure to air or oxygen a distinct flame being seen playing on the surface whilst water is formed.In one experiment a product thus pre- pared contained 91.1 per cent. of metallic vanadium (0.354 substance gave 0.574 grm. V,O,). This substance exposed for some weeks to dry air slowly absorbed oxygen and on roast-ing gave a percentage increase of 53-75 (0.453 grm. yielded 0.6965 V,O,) whilst 0.034 grm. or 7.5 per cent. of water was at the same time formed. This shows that the point of oxida-tion at which the metal containing hydrogen becomes stable in dq air corresponds nearly to the oxide V,O. A similar slow change in the appearance of the metal has been noticed in some portions of the metallic powder placed on microscopic slides.11. VANADIUX AKD BRONIKE. 1. Vanadium Oxyiribromide or IGmaclyl T&!mmiclP VOBr3 molec. wt. = 307*3.-When the vapour of perfectly dry and ROSCOE'S RESEARCHES ON VANADIUM. pure bromine is passed over vanadium trioxide (V,O,) heated to redness dense yellowish-white fumes of the oxytribromide are formed in the heated portion of the tube and these con- dense together with the excess of bromiue to form a dark red transparent liquid. In order to free the oxytribromide from excess of bromine the mixed liquids must be rectified in cucuo as the temperature of decomposition of the oxybromide lies (under the ordinary atmospheric pressure) below its boiling-point.By distilling under a pressure of 106 millims. of mercury in a current of perfectly dry air the whole of the bromine was got rid of before the thermometer rose to 45' C. The trans- parent liquid remaining in the retort had a dark red colour gave off white fumes on exposure to moist air and when thrown into water produced a light yellow solution of a vanadic salt. It is possible to distil the oxybromide under diminished pressure with but slight decomposition occurring although when heated under the atmospheric pressure it suddenly solidi- fies at 180' C. splitting up into the oxydibromide and bromine. Under a pressure of 100 millims. of mercury the oxytribromide volatilizes without decomposition between 130' to 136O C.The following analytical results were obtained:-Analysis No. 1 was made from a portion of oxytribromide which had not been dis-tilled ; No. 2 from a portion of the same substance after further treatment with dry air at 63'; No. 3 from another preparation which had been distilled in vucuo and in which the bromine determination is too high owing to traces of free bromine. The composition of the oxytribromide is as follows :-Calculated. Found. Mean. 7-I I. 11. 111. Y V = 51.3 16.6'3 16.52 16.87 16.62 16.67 Br = 240.0 78-10 79.62 79-10 80.48 79.36 0 = 16.0 5.21 7 --307-3 100*00 The colour of the oxytribromideis somewhat redder than that of bromine and it is more transparent in thin hlins and much more translucent than bromine.The oxytribromide slowly decomposes at the ordinary atmo- spheric temperature into bromine and oxydibromide; it is very deliquescent and hygroscopic and cannot be formed in presence ROSCOE'S RESEARCHES ON VANADIUM. of moisture. The specific gravity of the oxytribromide at 0' is 2.9673 and at 14'05 it is 2.9325. 2. Vanadium Oxydibromideor VunadylDibromide VOBr, molec. wt. = 227*3.-This substance forms suddenly when the oxytri- bromide is heated to temperatures above MOO and it is slowly produced by the same decomposition at lower temperatures. The oxydibromide is a yellowish-brown solid body in appear- ance resembling ochre; it is very deliquescent and on heating in the air it loses all its bromine and is converted into the pentoxide.Thrown into water it dissolves furnishing a blue solution of hypo-vanadic (V,O,) salt. Its composition is as follows :-- Calculated. Found. Mean. V .... 51-3 22.57 23*40 21-50 22-45 Br,. ... 0 .... 160.0 16.0 70.39 7.04 71.75 - 70.11 - 70.93 - - -7- 227.3 100.00 3. Vunadium T?ibrornide VBr, molec. wt. = 291.3.-This body condenses as a greyish black opikque amorphous subli- mate when dry bromine vapour is passed in excess over vanadium nitride heated to redness. Brown vapours are given off which soon condense in the cooler portions of the tube. The tribromide is a very unstable compound losing bromine even at the ordinary temperature in dry air and being con- verted into V,O when gently heated. It deliquesces rapidly on exposure to moist air giving rise to a brown liquid in this respect resembling the tricliloride; but on addition of a few drops of hydrochloric acid the brown liquid changes to the green colour characteristic of a solution of vsnadous salt (V,O,).No free bromine is evolved when the tribromide dis-solves in water. In order to prepare the tribromide pure nitride of vanadium contained in a porcelain boat was intro- duced into a combustion tube and after all the air had been displaced by dry carbonic acid the part of the tube containing the nitride was heated to redness the other part of the tube being kept at such a temperature as to volatilize any excess of bromine which might pass over. After all the nitride had burnt away the bulb containing the bromine was sealed off and a current of dry carbonic acid passed over the solid bromide ROSCOE’S RESEARCHES ON VANADIUM.to displace all traces of free bromine. A second method of pre-paring the tribromide is to pass bromine vapour over a mixture of vanadium trioxide and charcoal; in this reaction the oxytri- bromide is first formed then the oxydibromide and lastly the tribromide VBr,; but this plan is not to be recommended as the tube soon becomes stopped up by the formation of these solid compounds. The bromide thus prepared mas not analysed but it presented exactly the same appearance and properties as the tribromide obtained by the first method. No higher compound of bromine and vanadium than the tri- bromide could be obtained.The volatile liquid passing into the bulb in the first preparation was carefully rectified and it was all found to distil over at the boiling point of bromine leaving only a small quantity of the tribromide in the bulb. Some difficulty was experienced in obtaining satisfactory ana- lytical results with the tribromide owing to the fact already observed by Stas,* that bromide of sillrer when boiled with excess of nitrate of silver carries down with it some of this latter salt inclosed in the bromide and that this impurity cannot be got rid of by washing. Owing to this admixture of nitrate of silver the bromine determinations usually come out about two per cent. too high whilst the vanadium determinations gave constant numbers agreeing much more nearly with the calculated results.Thus in four analyses of the tribromide prepared on different occasitjns the mean percentage of bro- mine was found to be 84-15 the calculated percentage being $2.4 ;whilst the vanadium determinatioiis of the same portions gave 18.57 per cent. iustead of 17.6 per cent. In order to lessen as much as possible this error the precipitated bromide of silver was reduced in hydrogen until no further diminution of weight occuri*ed and the percentage of bromine ca,lculated from this loss. Calculated. E’ound. Mean. -I/ V = 51.3 17.6 18.46 18.80 18-53 18.59 Br = 240.0 S2-4 81-21 80.58 80.78 80.86 291.3 100-0 98-67 99.38 99-30 99-45 Experiments made with the bromine employed which had been rectified over potassium bromide and was carefully tested Y Xtas Recherches sur les Lois des Proportions chimiques p.156. ROSCOE'S RESEARCHES ON VANADIUM. for chlorine and iodine and shown to be pure proved that a similar excess of weight occurred on precipitation with nitrate of silver. In one experiment the percentage of bromine thus found was 100.96 and in a second experiment 101.41. The bromine determinations of the oxybromides are similarly all too high from the same came. 111. VANADIUM AND IODINE. When vapour of iodine is passed over the red-hot nitride of vanadium contained in a tube no action whatever takes place the nitride after the operation remaining perfectly un- changed. Vanadium trioxide is likewise unacted upon by iodine at all temperatures.IV. METALLIC VANADATES. In the first part of these researches" I pointed out (1) that the vanadates analysed by Berzelius prepared by boiling vanadic acid with the alkaline hydroxides and by double de- composition must be considered as meta- or monobasic vana- dates (2) that the so-called bi-vanadates aiialysed by Von Hauer,t and prepared by acting on the metavanadates with acids are anhydro-salts and (3) that the naturally occurring vanadates are tribasic salts and tht sodium ortho-vanadate is formed when one molecule of vanadium pentoxide is fused with three molecules of carbonate of soda three molecules of carbon dioxide being expelled. I have now to describe the preparation and properties of some characteristic members of these three classes of vanadates as well as those of a fourth new class viz.the tetrabasic or pyro-vanadates. Determination of ?7amdium in the Xoldle Vanadates.-The separation of vanadic acid from the metals of the alkalies by means of chloride of ammonium as proposed by Von Hauer is apt to give too low results both as regards the vanadium and the alkali. It is almost impossible to prevent traces of amnio-nium metavanadate from dissolving and on ignition even with the greatest care some portions of the finely-divided vanadium pentovide are invariably carried off when the aminonia escapes. * Philosophical Transactions 1868 (Baherian Lecture) ; C'hcm. SOC.J.[a] vi 322. +-Jonm. prac. Chem. Bd. lxix p. 355 1536. ROSCOE'S RESEARCHES ON VANADIUM.On the other hand the volatilization of the comparatively large quantities of sal-ammoniac which must be employed in order to ensure the complete precipitation of the vanadium almost always entails a considerable loss of the fixed alkaline chlo- rides. A far more accurate plan for the separation of vanadium is the precipitation of the soluble vanadate by acetate of lead when basic lead vanadate is precipitated which is so insoluble that a portion when finely powdered and boiled in water did not dissolve in sufficient quantity to enable the lead to be detected in th'e filtrate with sulphuretted hydrogen. This salt is also insoluble in acetic but dissolves readily in nitric acid liberating vanadic acid which separates out but dissolves completely when the liquid is warmed.In the analysis of a soluble vanadate this iiisoluble lead salt is collected on a filter dried at 100' C. and weighed; a given quantity of the dried salt is then dissolved in nitric acid the lead precipitated by pure sulphuric acid and the lead sulphate determined with the usual precautions of evaporation with addition of alcohol &c. The lead sulphate thus obtained is. (contrary to B er zelius's statement) quite free from vanadium whilst the vanadic acid in the filtrate is obtained perfectly pure and well crystallised on evaporation and ignition. The filtrate from the lead vana-date freed from excem of lead by nieans of sulphuric acid and evaporated yields the alkaline sulphate not containing a trace of vanadium.Sodium Vanadates. 1. Sodium Ortl~ovanadate,Na,VO +lGH,O.-When a mixture of three molecules of sodium carbonate and one molecule of vanadium pe'ntoxide is fiised until no further evolution of carbon dioxide is observed three molecules of CO have been expelled and a tribasic vanadate remains as a white crystalline mass. In one experiment in which a slight excess of sodium car- bonate was taken 0.5785 grm. V,O liberated on fusion 0.4185 grm. COT According to the equation- the weiglt of CO liberated by this quantity of vanadium pentoxide is 0.4182 grm. The mixture is easily fiisible at fist but becomes less so as ROSCOE’S RESEARCHES ON VANADIUM. the reaction proceeds; whilst to begin with the heat of a Bunsen’s burner is sufficient to melt the mass it is necessary to apply the heat of a blowpipe-flame to keep up the fusion when the decomposition becomes more nearly complete.On cooling the solidified mass acquires first a dark green colour and then passes through yellow until when cold it ‘becomes perfectly white and is found to possess a crystalline appear-ance. It dissolves easily in cold water but is insoluble in alcohol. Hot water must not be employed for dissolving the fused mass and as little cold water as possible. The cold strong aqueous solution must be instantly mixed with excess of strong alcohol ; two layers of liquid are then formed the upper one consisting of dilute alcohol the lower one of the saline solution. After standing for a fern hours the lower layer of liquid solidifies forming an aggregate of colourless needle-shaped crystals.These crystals which possess a strong alkaline reaction are washed with small quantities of alcohol then placed on a porous plate over sulphuric acid in vacuo and after remaining for a short time they may be taken out for analysis. The analysis yielded the following results :-Calculated. Found. Na,. ... 69.0 14-61 13-80per cent. V.... .. 51-3 10.86 10.86 ) 0 .. . . 64-0 13.56 -16H20.. 288.0 60.97 60.44 , 472.3 100*00 Sodium orthovanadate is an extremely unstable compound. Its aqueous solution slowly undergoes decomposition on stand-ing at the ordinary temperature of the air out of contact with atmospheric carbonic acid whilst at higher temperatures the same change takes place quickly.This decomposition consists in the formation of a new salt sodium tetravanadate the liquid becoming strongly alkaline whilst caustic soda is liberated according to the equation- 2(Na,VO,) + H,O = Na,V,O + 2NaHO. This remarkable reaction was carefully investigated as is seen in the sequel. I have not been successful in several attempts to prepare a ROSCOE’S RESEARCRES ON VANADIUM. tribasic sodium vanadate containing basic hydrogen. All the reactions which with the corresponding phosphates yield hydrogen-sodium salts give with the vanadate the tetrabasic compound above mentioned. The orthovanadates of most of the metals are insoluble compounds obtained by precipitating neutral solutions of the soluble metallic salts with a solution of orthovanadate of sodium.The reactions of the more important metals are as follows :-Reaction of the Orthovanndates. 1. Ferric salt .,. . . . Gelatinous precipitate of a light brownish -yellow coloui; soluble in hydrochloric insoluble in acetic acid. 2. Ferrous salt ..... Dark grey precipitate. 3. Manganous salt . . Brownish-yellow crystalline precipitate. 4. Zinc salt .. .., ,. White gelatinous precipitate. 5. Cobalt salt . . . ... Brown-grey gelatinous precipitate. 6. Nickel salt . . . . . . Canary-yellow crystalline precipitate. 7. Aluminium salt . . Bright yellow gelatinous precipitate soluble in excess of both reagents ; on boiling a white precipitate is again thrown down.8. Copper salt ...,.. Apple-green precipitate. 9. Mercuric salt .. . . Orange-yellow precipitate. The reaction which Serves best to distinguish the ortho- from the inetavanadates is that of the corresponding copper salts. Orthovanadate of copper possesses a bright apple-green colour whilst the metavanadate falls down a light yellow crystalline powder. 2. Tetrasodium Vanadate or Pyrovanadate Na,V,O +18H20.-This salt crystallises in beautiful six-sided tables. It is easily soluble in water insoluble in alcohol and is precipitated from aqueous solutions by the latter Iiquia in the form of white scales of a pearly lustre. The pyrovanadate can be readily obtained by fusing one molecule of vanadium pentoxide (V,O,) with two molecules of sodium carbonate (Na,CO,) dissolving and crystal- lising.It can also be obtained by the deconiposition of the orthovanadate in aqueous solution. As long as the tetrabasic salt contains free alkali from the decomposition of the ortho- ROSCOE’S RESEARCHES ON VANADIUM. vanadate the precipitate with alcohol forms oily drops which golidify after some time only whilst the pure salt is at once thrown down in the form of silky scales. If the fusion of vana-dium pentoxide with three molecules of carbonate of soda be not completed at a very high temperature the carbonate is not fully decomposed and the fused mass when dissolved in water crystallises at once in six-sided tables or if the solution be very concentrated in nodular groups of needle-shaped crystals.The tetrabasic salt is more easily fusible than the tribasic salt and on cooling from fusion it also forms a crystalline mass. - Calculated. Found. Mean. Na ,... 92.0 V2...... 102.6 0,....,. 112.0 14.58 16.27 17’77 /14-67 16.29 - 14.79 15.71 - 1457 15.60 - -16.19 - \ -16.06 - 14-68 16.06 - 18H20,. 324.0 51.38 50.69 63.M 51.44 - - 51.84 630.6 100.00 When a solution of tetrasodium vanadate is treated with carbonic acid the salt is decomposed into sodium carbonate which crystallizes out and sodium metavaaadate which being the more soluble salt remains in solution; thus :-Na4V207 + GO = 2NaV03 + Na2C03. The insoluble py-rovanadates precipitated in solutions of the various metals possess properties generally similar to those of the corresponding tribasic vanadates.Calcium Vanadates. If to a freshly prepared solution of trisodium vanadate a solution of chloride of calcium be added a white precipitate falls down whilst the liquid possesses a strongly alkaline re- action and absorbs carboiiic acid from the air. The precipitate is a mixture of calcium pyrovanadate and calcium hydroxide; the tribasic calcium salt therefore cannot thus be obtained as it at once decomposes as follows :-Ca3V,0 + H,O = Ca,V207 + CaH20,. Calcium Pyrovanadate Ca,V,07 +2iH20.-This compound is precipitated as a white amorphous powder when a solution of ROSCOE'S RESEARCHES ON VANADIUM. chloride of calcium is added to one of the tetrabasic sodium salt. The salt dried at loo0 C.exhibited the following corn-position :-Calculated. Found. / A -Ca ........ 80.0 23.56 23-23 V,. ......... 102.6 30.21 30.16 0,.......... 112.0 32.98 - 2,1H20.. .... 45-0 13.25 12.63 339.6 100*00 Ban'um Pyrovanadate Ba,V,O,.-The dibasic barium salt is anhydrous but otherwise it closely resembles the corresponding calcium compound. It is slightly soluble in water. For analysis it was dried at 100" C. Calculated. Found. -Ba ........ 274.0 56-08 54-69 V,. ......... 102.6 20.99 21-50 1124 22-93 -0,........... -- 488.6 100~00 Lead Thiadates. Three native lead vanadates are known. (a) Lead metavanadate Pb(VO,), occurs as Dechenite. (b) Lead pyrovanadate Pb,V,07 occurs as Descloizite. (c) Lead orthovanadate and lead chloride 3Pb,(VO,) + PbCI, occurs as vanadinite.1. Basic Pyrovanadate qf Lead 2Pb,V,07 + Ph0.-TVhen a solution of the tetra-sodium vanadate is mixed with a solution of lead acetate a pale yellow precipitate is thrown down and the liquid acquires an acid reaction. The properties of this salt have already been described. For analysis the salt was dissolved in nitric acid and (with the exception of No. 1)the lead precipitated by sulphuric acid. The sulphate of lead was found to be quite free from vanadium and the vauadic acid contained no lead provided care had been taken to remove all nitric acid by evaporation and if the liquid was mixed with alcohol before the lead sulphate was filtered. VOL. XXIV. D ROSCOE'S RESEARCHES ON VANADIUM.34 Calculated. Paund. Mean. A Pb ,... 1035.0 69-92 50.92 69.85 69.83 70.57 70.29 V,. . .... 205-2 1386 13.55 12.98 13.52 13-03 13*27 015. . .. 240.0 16-22 ---. 1480.2 1OO*OO 2 Lead Orthovanadate Pb,(VO,),.-The tribasic vanadate of lead falls as an insoluble nearly white powder when tribasic sodium salt is precipitated by lead acetate. 0.7245 of the sub-stance when decomposed by nitric acid and precipitated by sulphuric acid yielded 0.1515 of V,O, or contained 11.75 per cent. of vanadium9 the percentage required by the formula being 12.04 3. Lead Orthoomadate and Lead Chloride ;arttjicial Vanadinite 3(Pb,(V O,),)PbCl, or lead trivanado-chlorhy din 2 3v0"'1 Pb, If'oxide of lead vanadic acid and chloride of lead be fused together for a few hours in the proportions in which they are contained in the above formula the mass after slowly cooliiig is found to consist of a greyish-yellow crystalline substance in the interstices of which groups of needle-shaped crystals occur.The fused mass on boiling in water is soon reduced to a powder entirely consisting of fine crystals. This crystalline powder is boiled with water until no further trace of chlorine can be detected in the washings when it is dried ready for analysis. The crystals obtained were too small for measurement ; they were however seen to consist of hexagonal prisms ; the faces of the hexagonal pyramid could not be identified. The crystals have a yellow colour and possess the waxy lustre characteristic of the natural mineral.The following gives the composition of various specimen8 of natural vanadiniles compared with that of the artificial mineral :-Naturd ranadinites. Artificial Calculated. dimapan TViuddlka$l Wleklow. Beresesow2k vanadinites* 3(Pb,(T0,),)PbCl2. (Berzelius). (Rammelsberg). (Struve). il>r(zi Lead.. . . .. 73-08 70-40 71'20 68'72 73.76 71.96 71-57 Vanadium . 10.86 -9.77 13.15 9-54 11.11 -Phosphorus. ---1.34 -Chlorine . . 2-56 2.54 2.23 2.44 2.46 2.33 2.17 I Oxygen.. .. 13-55 --- ROSCOE'S RESEARCHES ON VANADIUM. The specific gravity of the artificial vanadinite at 12' C. ie 6.707 that of the natural mineral varies from 6.66 to 7.2*. Silver Vanadates I. Silver Orthovanadate or Tribasic Silver Vanadate Ag,VO, is precipitated as a deep orange-coloured powder when a freshly prepared solution of tribasic sodium salt is mixed with a perfectly neutral solution of silver nitrate.If the precaution of neutralizing the silver solution with carbonate of soda filtering and boiling be not adopted a salt ie precipitated which consists of a mixture of tribasic and tetrabasic silver salt. The colour of this mixed salt is lighter than that of the tribasic compound and it gives on analysis a percentage of silver and vanadium intermediate between the two salts. Silver orthovanadate is easily soluble in nitric acid and am- monia. For analysis it was dissolved in nitric acid the silver being precipitated as chloride and the vanadium estimated in the filtrate.Calculated. Found. Mean. Ag .. 324.0 73.75 74.12 73-54 73.83 V.. .. 51.3 11-67 11-59 11.94 11.86 0,.... 64.0 14.58 --439.3 looooo 2. Tetrabasic Silver Vanadate Ag,V,07.-This salt is pre-pared by precipitating a solution of pure tetrasodium salt with a neutral golution of silver nitrate. It is a dense yellow pre- cipitate settling very easily when the liquid is warmed and resembling in its appearance ordinary tribasic phosphate of ~ silver. Calculated. Found. Ag .......... 432.0 66-81 66.45 V ............ 102.6 15.87 15.99 O,.. .......... 112-0 17.32 - 646% 100*00 * Pyromorphite and apatite were prepared artificially for the &st time in 1852 by Manross (Ann. Ch. Pharm. lxxxii p. SeS) and afterwards by Deville and Caron and Debray.Mimetesite has also been recently artificially prepared by Lechartier (Comptes Rendus 1867 lxv p. 1'72). ROSCOE’S RESEARU~SON VANADIUM. From the foregoing experimentrs on the vanadats it appears (lj That the soluble tribasic salts are less stable at the ordinary temperature than the tetrtlbasic compound Na,VO, splitting up in solution into free caustic soda and the pyro- aalt. (2) That at a high temperature on the other hand the tri-basic form is the most stable V,O liberating three molemilea of CO when fused with carbonate of soda but forming a mono-basic (meta) salt when boiled wit,h a solution of alkaline carbonate. (3) That as the majority of the naturally occurring vanadates are tribasic compounds we may assume that these have been produced at a high temperature.(4) That in aqueous solutions the soluble pyrovanadates are easily decomposed by carbonic acid into an alkaline carbonate and a monobasic or metavanadate. Hence the order of stability of the different vanadatea a& the ordinary temperatures is as follows :-(1) Monobasic or metavanadates. (2) Tetrabasic or pyrovanadates. (3) Tribasic or orthovanadates. 111the phosphorus series the order of stability is (as is well known) exactly the reverse of this the tribasic phosphoric acid and soluble orthophosphates being most stable and being formed from the other two classes of acids and soluble salts either by ebullition alone or in presence of weak acids.

ISSN:0368-1769    

DOI:10.1039/JS8712400023

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

37 N.-On some New Derivatives of Coamarin. By W. H. PERKIN, F.R.S. INMay last I had the honour of laying before the Societya short account of some derivatives of this interesting product. Since thar time I have procured further information upon the sub- stances I then described and have also obtained a number of new derivatives of coumarin. I now beg leave to bring an account of my results before the Society. Dibromide of Cozimarin. When preparing this product I originally mixed a solution of coumarin in disulphide of carbon with a similar solution of bro-mine using these substances in theoretical proportions The resulting solution mas then allowed to evaporate spontaneously and the product purified. By this method I obtained a very poor yield of the dibromide.I have since found that if the solution of bromine and coumarin be kept for twelve hours or more previous to the evaporation of the disulphide a much larger yield of product is obtained 5 grms. of coumarin gener- ally yielding from '7& to 8 grms. of dibromide. Dibromide of coumarin when mixed with an alcoholic solu- tion of potassic iodide becomes brown and on evaporation deposits metallic-looking needles apparently consisting of a mixture of iodine and coumarin crystallised together. u. Brornocounaarin. Upon referring to the previous method given for the pre paration of this body it will be found that it wa8 obtainedfiom the mother-liquors of dibromocoumarh. If however a mixture of bromine and coumaiin (mixed with disulphide of carbon) in the proportion of two parts of the former to one of the latter be heated in a sealed tube to about 200' C.for three or four hours the resulting product will consist almost entirely of monobromocoumarh. In this reaction dibromocoumarin is undoubtedly first pro- duced but at the high temperature employed it is decomposed VOL. xxxv. E PERKIN ON SOME NEW by the hydrobromic acid produced losing half of its bromine thus-C,H,Br,O + HBr = CSH,BrO + BrBr. Dibromocoumarin. Bromocoumarin. The bromocoumarin obtained by this process sometimes crystallises from alcohol in long slender needles ; these how- ever on standing in the mother-liquor for a few days become short and hard like those described in my previous paper; in fact so different was the appearance of this body when freshly crystallised from that which 1had previously obtained that I sub-jected it to analysis.The following are the results obtained :-I. -4440 of substance gave -3710 of AgBr. 11. -3436 of substance gave *5986of CO, and *0702of H,O. Theory. Experiment. # h -. I. 11. C .... 108 48.00 -47.51 H .... 5 2.22 -2.2 7 Br .... 80 35.56 35-56 -14-22 -0 .... 32 -225 100*00 I have however found a still more simple process for the preparation of bromocoumarin than the above. It consists in the decomposition of the dibrornide of coumarin wit11 alkalies the following reaction taking place :-CI,H,O,,Br + KHO = C9H,Br0 + KBr + H,O. Dibromide of coumarin. Bromocoumarin.When this process is employed the dibromide of coumarin is powdered and suspended in alcohol and rather more than enough alcoholic potash is added than is required to complete the above reaction. The decomposition takes place rapidly the mixture becoming quite hot and of a pale yellow colour. After it has stood for some time water is gradually added until it ceases to throw down any more bromocoumarin. When sufficiently diluted the product is collected upon a filter washed DERIVATIVES OF COUMARIN. dried and crystallised from spirit. In this way it is generally obtained in transparent needles about half-an-inch in length. An analysis of this product gave the following numbers :--4102 of substance gave *7242 of CO, and *0872of H,O.Theory. h - Exp. c .......... 108 48.00 48.15 H .......... 5 2.22 2-36 Br .......... 80 35.56 0 .......... 32 14-22 225 100*00 The alkaline filtrate from the above contains a quantity of this substance in solution which may be precipitated with acid and if a large excess of alkali has been used most of the bro- mocoumarin will be found in solution ; it is however apparently not usually so pure as that precipitated with water and gener- ally forms smaller crystals. From the difference in the appearance of the products ob-tained by the above processes I was at first inclined to think they were isomeric forms of bromocoumarin but as the melting points are nearly identical as are also the products of decom- position I am induced to believe that these variations are due to the presence of small amounta of impurities.a Bromocoumarin when left in contact with cold alcoholic ammonia decomposes with formation of ammonic bromide and a non-crystalline sticky mass easily soluble in water. Heated with potassic hydrate it yields potassic bromide and a new acid. It decomposes when heated with potassic cyanide and alcohol in a sealed tube forming a brown solution from which water throws clown a drab coloured amorphous precipitate. When it is heated with alcohol to 200' C. in a sealed tube for five or six hours slight decomposition takes place with formation of hydrobromic acid A similar change takes place if water be used instead of alcohol. a. Uibromocournarin. The method I previously gave for the preparation of this body consisted in heating in a sealed tube to 140' C.a mixture E2 PEREIN ON SOME NEW of one part of coumarin two parts of bromine and four or five parts of disulphide of carbon. I have since found however that this process is greatly improved by the addition of iodine to the mixture as it is then only necessary to heat the sealed tube for four or five hours in a bath of salt and water to com-plete the reaction. The procinct is freed from disulphide of carbon by evaporation and from iodine by means of a solution of potassic iodide and finally purified by two or three crystalli- sations fi-om alcohol. A specimen prepared in this manner gave the following numbers :--2584 of substance gave *3330of CO and -0371 of H,O.Theory. Exp. C .......... 108 ~ 35.53 35.15 H ......... 4 1.31 1-59 Br .......... 160 52-63 - 0 .......... 32 10.53 L__- 304 100*00 The melting point of this substance is 183' C. and not 174' C. as I previously gave it. It is however not so definite as might be desired as it generally shows signs of fusion below 183O C. u Dibromocoumarin is easily decomposed by boiling alcoholic or aqueous potassic hydrate with formation of potassic bromide and the gotassic salt of a new acid. When suspended in cold alcoholic ammonia 01 dibromocou-marin becomes of a pale yellow colour and gradually dissolves with formation of animonic bromide ; on standing a Crystalline product is deposited. It is volatile when heated and evolves ammonia when treated with potash.The resulting alkaline solution does not deposit any product when acidified. It is soluble in water and crystallises in beautiful white needles. The alcoholic solution upon evaporation yields a second crystalline body soluble in water. It cannot be volatilized without undergoing decomposition. A syrupy body is alao produced. I hope to return to the examination of these products at a future period. DERIVATIVES OF COUMARIN. p Bromocoumarin. It will be remembered that the sodium derivative of the hydride of salicyl when digested with acetic anhydride yields ordinary coumarin. It therefore appeared to be of interest to treat the sodium compound of brominated hydride of salicyl in a similar manner to see whether a brominated coumarin could be obtained.The hydride of sodium-bromosalicyl when submitted to the action of acetic anhydride rapidly changes colour and dissolves the mixture becoming quite hot. After the reaction has mode- rated the product is well boiled for ten or fifteen minutes and then poured into water in which it sinks as a heavy oil acetate of sodium dissolving. On distilling this oil acetic an- hydride and acetic acid first come over then a quantity of oily product which rapidly solidifies ; the first half of this contains a large quantity of the hydride of bromosalicyl the remaining portion however when crystallised from alcohol two or three times yields col ourless flat prisms apparently rhombic. This substance gave the following numbers on analysis :-I.*5170of substance gave -9071 of CO, and -1036 of H,O. 11. 03576of substance gave -6276 of CO, and *0735of H,O. The numbers give percentages agreeing with those required by the formula- C9H5Br02 as the following comparisons will show :-Theory. Experiment. y-'I. 'Y 11. C .... 108 48.00 47.84 47-86 H .... 5 2-22 2-22 2.28 Br .... 80 35-56 c 0 .... 32 14.22 -225 100~00 This substance is therefore monobromoco~mar~n.It is PERKIN ON SOME NEW moderately soluble iii spirit and when fused has an odour some- what similar to that of coumarin. It greatly differs in properties from the bromocoumarin previously described. Its melting point is 160' C. or 50 degrees higher and when boiled with alcoholic or aqueous potassic hydrate it does not decompose with formation of potassic bromide but simply dissolves like ordinary coumarin I have therefore termed it p bromocou-marin.p Dibromocoumarin. On treating the hydride of sodium-dzlxomosalicyl with acetic anhydride in exactly the same manner as for the preparation of bromocouniarin a beautifully crystalline product is ob-tained. It gave the following numbers on analysis :-I =3639of substance gave- 04714of CO and -0463 of H,O 11. 02080of substance gave- 9623 of GO2 and 00266of H20. These numbers give per centages agreeing with those re- quired by the formula- C9H41Jr202 as will be seen by the following comparison :-Theory. Experimeiit. h v 11.C .... 108 35.53 35.33 35.41 H .... 4 1.31 1.41 1-46 Br .... 160 52.63 -0 .... -32 10.53 -304 100~@0 The substance is therefore dibromocoumarin. It is rather difficultly soluble in alcohol. It crystallises in short hard needles. It is not the same body as that obtained by acting on coumarin with bromine and iodine. It melts at 176' C. and is not decomposed by boiling with a solution of potassic hydrate. I have therefore designated it as dibromocoumarin. DERIVATIVES OF COUMARIN. Dichloride of Counzarin. A solution of coumarin in chloroform absorbs chlorine gas very minute quantities of hydrochloric acid being formed. On allowing the solution to evaporate spontaneously after the chlorine has been passed through it for an hour or two a syrupy product is obtained very like new honey.This is the dichloride of coumarin. I have not analysed it as there is no way of judging of its purity; but from its products of decom-position there can be no doubt that it possesses the formula- C&4p,,C1,. On keeping it appears to decompose; when heated it gives off hydrochloric acid and on distillation is converted into chlorocoumarin. With a1 coholic potash it decomposes in the same way as the dibromide. a. Chlorocournarin. When a mixture of one part of coumarin and three parts of pentachloride of phosphorus is heated in a retort placed in an oil-bath the two bodies slowly react upon each other as the temperature rises and when the oil has reached about 200°C. the product becomes a dark brown liquid (at a few degrees higher it is converted into a carbonaceous mass) ; during this reaction a volatile liquid consisting chiefly of terchloride of phosphorus distils over.The contents of the retort after treatment with water become a pasty mass of crystals which is first purified by distillation and then by several crystallisations fiom alcohol. The substance gave the following numbers on analysis :-1. 03904of substance gave- 3546 of CO and *I050of H,O. 11. 04006of substance gave- -8760 of CO and 01047of H,O. 111. 03364of substance gave- *2703of AgC1. These numbers give percentages agreeing with those re- quired by the formula- C,H,ClO,. PERKIN ON SOME hiW The following is a comparison of the theoretical and experi- mental numbers- Theory.Experiment. F -I. 11. 111. -C . . .. 108.0 59-83 59.70 59-64 H .... 5.0 2.77 2-98 2.90 -C1 .... 35.5 19.67 -19-88 0 .... 32.0 17.73 -I --c-180.5 100*00 From these results it is evident that the pentachloride of phosphorus has simply given up chlorine to the coumarin. It is very curious that if half the amount of pentachloride of phosphorus mentioned above be employed the product of the reaction suddenly carbonizes sometimes when the oil-bath is at a temperature as low as 150'C. I have had this happen twice whereas with the excess of pentachloride the product may be heated in an oil-bath standing at 200' C. Chlorocoumarin may be easily prepared by treating the dichloride of coumarin with alcoholic potash in exactly the same manner as described for the preparation of ct bromocou-rnarin the reaction being analogous- CgH60,C12 + KHO = C,H5C10 + KC1 + H,O.Dichloride of coumarin. Chlorocoumarin. Obtained by either of the above processes this substance forms flat needles about half an inch long. It is moderately soluble in alcohol and slightly so in hot water from which it crystallises on cooling. It melts at 122°-1230 C. and when heated emits an agree- able aromatic odour. When boiled with alcoholic potassic hydrate it decomposes with formation of potassic chloride and forms the same product as a bromocoumarin when treated in the same manner. From this description ct chlorocoumarin is evidently a sub-stance difl'erent fiom that obtained by Dr.Basecke his product is in fdct the 6 chlorocoumarin corresponding to the bromo-coumarin and was obtained fiom the hydride of chlorosalicyl. DERIVATIVES OF COUMARIN. Tetrachlorocoumarin. Chloriiie gas when passed through a solution of coilmarin and iodine in tetrachloride of carbon is rapidly absorbed hydrochloric acid being evolved; if the gas be passed for two or three hours a quantityof a reddish body separates on evaporat- ing the product so as to separate the tetrachloride of carbon an oily residue is obtained the red substance having fused with the impurities. On mixing this substance with alcohol it soon becomes a white paste. This is then pressed in a small linen bag when a white product is obtained which is further purified by being several times crystallised fiom spirit.It gave the following numbers on analysis :--3877 of substance gave- 05309of C02 and *0355of H,O. These numbers give per centages approximating to those required by the formula- C,H2c1402 arJ will be seen from the following comparison :-Theory. EX~. -C9 .......... 108 38.03 37.32 H .......... 2 0.70 1-02 C14 .......... 142 50.00 - 0 .......... 32 11-27 - -284 100-00 It is therefore a tetrachlorocoumarin. This siibstance melts at 144'-145' @. It is difficultly soluble in spirit from which it crystallises in small white needles. When heated with alcoholic potassic hydrate it decomposes with formation of potassic chloride and the salt of a new acid not yet examined.Coumarilic Acid. I have already mentioned that tc bromocoumarin when boiled with a solution of potassic hydrate decomposes yielding potassic bromide and the aalt of a new acid. To prepare this acid in a PERKIN ON SOME NEW pure atate I have found it beat to proceed in the following manner A quantity of pure tc brornocoumarin is mixed with an excess of the ordinary solution of potassic hydrate. On heating this mixture the bromocouniariii gradually dissolves but on reaching the boiling-point the solution rapidly becomes a pasty crystalline mass. Sufficient water is then added to dissolve this and the boiling continued for about an hour. The solution on cooling deposits the potassic salt of the new acid in small needles.If any quantity of this salt remains in the mother- liquor the addition of potassic hydrate will precipitate it. The crystalline salt thus obtained is collected upon a linen filter and well pressed to remove as much of the alkaline-mother liquor as possible. It is then crystallised once or twice from alcohol and dried. To obtain the acid from this salt it is dissolved in water and hydrochloric acid is added in excess. The new acid is then thrown down as a snow white crystalline precipitate which is purified first by washing with water on a filter and then by cry stallisation from boiling water. It gave the following numbers on analysis :-I. 9112 of substance gave- 05146of CO and -0734 of H,O. 11. 9561 of substance gave- 06266of CO and -0846 of H26.These percentages give numbers agreeing with bhose re-quired by the formula- %HBOS as the following compa.rison will show :-Theory. Experiment. / h \ r---\ I. 11. C .... 108 66.67 G 6-45 66-72 H .... 6 3.70 3.8 6 3.67 I 0 .... -48 29.63 -162 100*00 This acid which I have proposed to call coummdic acid melts at 192O-193OC. It distils without leaving any residue but decomposes partially with formation of an oily body smelling DERIVATIVES OF COUMARIN. like naphthaline. When gently heated it sublimes. The vapour is very suffocatinq. It is excessively soluble in alcohol but difficultly so in chloroform and disulphide of carbon. It is moderately soluble in boiling water from which it crysta11' ises on cooling in beautfful long needles like benzoic or cinnandc acid Its aqueous solution has a bitter taste.It is not decomposed when heated with potassic hydrate to 180O C. for an hour O! chlorocoumarin may be employed instead of cc bromocou-marin in the preparation of this acid. It is monobasic. dmrnonic Coumarilate.-This salt is easily obtained by dissolv- ing cournarilic acid in aqueous ammonia and evaporating in vacuo over sulphuric acid. It is a beautiful salt crystallising in flat prisms radiating from a commoii centre. It is easily soluble in water. Xodic Coumarilak.-Coumarilic acid dissolves in a solution of sodic carbonate with effervescence forming a salt which crys- tallises in transparent rectangular tables. It is easily soluble in water.Potassic Cozcrna&late.-The preparation of this salt has already been given. It is difficultly soluble in cold alcohol but moderately soluble in this menstruum when boiling ; nearly insoluble in solutions of potassic hydrate of about 20 per cent. It crystallises in pritJms half an inch long which break up into sinall plates. Its taste is bitter. A determination of the potas- sium in this salt gave the following numbers :-*1781of salt gave- -0759 of K,SO = 19-07per cent. of potassium. The formula C9H,K0 requires 19.5 per cent. of potassium. CaZcic Coumarilate is thrown down as a precipitate on addition of calcic chloride to potassic coumarilate. It is crys-talline and difficultly soluble in water. Baric Cournarilate is somewhat like the calcic compound.Afyentic Coumarilate. -On adding argentic nitrate to a solution of potassic coumarilate this salt is thrown down as a white curdy precipitate slightly soluble in water. The follow-ing determinations were made of the silver in this salt :-I. -1118of substance gave- *0443silver = 39.62 per cent. PERKIN ON SOME NEW 11. 01608of substance gave- -0648 of silver = 40.29. The formula C9H,Ag0 requires 40.15. Analysis I1 was made from coumarilic acid prepared from u chlorocoumarin 1 from u bromocoumarin. Plumbic Coumarilate is a white curdy precipitate. Mercurous Cownarilate is also a white precipitate. Ferric Coumarilate is a pale brown precipitate. BPQomocoumarilicAcid. This acid is produced in the same manner as coumarilic acid but substituting u dibromocoumarin for bromocoumarin.LY The acid is also purified by crystallisation from spirit and water instead of water. It gave on analysis the following numbers :-I. 02504of substance gave- -4109 of CO and *0489of H,O. 11. 93260 of substance gave- -5357 of CO and *0658of H,O. Thefire numbers give percentages agreeing with the formula- C9W5Br0, a8 the following comparison will show Theory. Experiment. 7-\ I. 11. C .... 108 44.81 44.75 44.82 H .... 5 2.08 2.17 2.24 Br .... 80 33-19 -0 .... 48 --19.92 241 100.00 I therefore propose to call this acid brornocoumnrilic acid; its formation may be expressed thus :-C9H,Rr,0 + H,O = C,H,BrO + HBr. Dibromocoumarin.Bromocoumarilic acid. Bromocoumarilic acid melts above 250' C It crystallises DERIVATIVES OF CUUMARIN. from a mixture of spirit and water in needles. It is very soluble in alcohol and but little so in water. When heated to 180' C. with potassic hydrate it decomposes and becomes brown potassic bromide being formed. It has a bitter taste andis monobasic. Ammonic Bromocozcmarilate is easily soluble in water and crystallises in needles. Sodic Bromocoumarilate is easily soluble in water but does iiot produce good crystals. Potassic Bromocoumari1ate.-This salt is prepared like the corresponding coumarilate. It is easily soluble in water but is almost wholly thrown down from its aqueous solution by strong solutions of potassic hydrate.It crystallises from alcohol in beautiful long needles. Determinations of the potassium in the salt gave the following numbers :-I. 03215 of substance gave- -1026 of K,SO =.14*30per cent. of K. 11. el897 of substance gave- *0600of K,SO = 14-17 per cent. of l<. The formula C9H,BrK0 requires 14-00per cent. of potassium. Bark Bromocoumarilate may be obtained by the addition of a solution of baric chloride to the above potassic salt as a crys- talline precipitate difficultly soluble in water. Argentic Bromocoumarilate is a white precipitate. Plumbic Bromocoumarilate is a white precipitate. Su@liocoumarilic Acid. On digesting a mixture of about one part of coumarin and five parts of fuming sulphuric acid in the water-bath for an ho& or two the product will be found to dissolve perfectly in water.This when diluted and neutralized with baric carbonate yields besides baric sulphate a soluble salt which when evaporated crystallises in tufts of transparent prisms. This is rendered pure by recrystallisation from water. To obtain the new acid from this salt it is dissolved in water and sulphuric acid added in exactly the quantity necessary to precipitate all the barium as sulphate. The solution is then filtered and evaporated first over the water-bath and then in vacuo. In this way the acid is usually obtained in needies easily soluble in water. It has not been burnt but from the PERKIN ON SOME NEW analysis of its salts its formula when anhydrous is C,H,O,SO,.Determinations of its water of crystallisation gave the following numbers :-I. 09330of crystallised acid lost 01305of water at 100°C. = 13.99 per cent. 11. 05635 of crystallised acid lost -0783 of water at 100' C. = 13.9 per cent. Ti1 one experiment I obtained this acid in octahedia which were very brilliant whilst in the mother-liquor but became opaque as soon as exposed to the air. A determination of the water of crystallisation gave the following results :-*3792of' substance lost 00527 of water at 100OC. = 13.90 per cent. This preparation when recrystallised was deposited on the palm of needles. It is therefore probable that they originally crystallised with more wat'*erthan is contained in the needles. These numbers correspond with those required by the formula-C9H60,S0,2H,0 which theoretically contains 13.74 per cent.of H20. The crystallised acid does not lose any more weight at 200' C. than at 100"C. This acid which I propose to call sulphocoumarilic acid possesses a strongly acid and bitter taste; it is very soluble in water and may be evaporated to a thin syrup before it shows any signs of crystallisation. It is monobasic. When its salts are mixed with an excess of alkali a yellow solution is obtained similar in appearance to that produced by dissolving coumarin in alkali. Ammonic Sull3J~ocournnrilate.-This salt is obtained by eva-porating a solution of the above acid to which an excess of ammonia has been added. It crystallises in satiny needles very soluble in water and also soluble in alcohol.Sodic SuZpJ2ocoumariZate.-On adding a solution of sodic carbo- nate to n solution of sulphocoumarilic acid effervescence takes place and on evaporating the resulting solution when neutral beautiful crystals are obtained very transparent and derived fkom the rhombic octahedron. It is easily soluble in water but nearly insoluble in alcohol. DERIVATIVES OF COUJIARIN. Potassic Sulphocoumarilate crystallises in flat prisins easily soluble in water insoluble or nearly so in alcohol. Ba& Xu113hocournarilate.-The preparation of this salt has already been given. It contains a considerable quantity of water of crystallisation the crystals efflorescing rapid17 in vacuo. The formula is-C,,Iq,,O43a"~S0,5H,O as the following results will diow :-I.1.0232 of crystallised salt lost in vacuo-*lo67 of H,O = 1043 per cent. and from vacuo to 18OOC. *0279= 2-90 per cent. IT. 07420of crystallised salt lost in vacuo-00777 of H,O = 10.50 per cent. and from vacuo to 180 00198= 2.66 per cent. These numbers show that this salt loses four molecules of water in vacuo the fifth being given off entirely at 18OOC. Theory. Experiment. 11.-' I. 1 4 mol. ...... 10.63 10.43 10.50 1mol. ...... 2-66 2.90 2.66 Determinations of' baiium in the anhydrous salt gave the following numbers :-I. 02456of substance gave- -0969 of baric siilphate = 23-20 per cent. of barium. 11. *1192 of substance gave- -0474 of bark sulphate = 23.38 per cent. of barium. 111.*0994of substance gave- *0393of baric sulphate = 23.25 per cent. of barium. The formula C,,H,,04Ba"2S0 requires 23.34 per cent. of barium. Combustion of barium salt containing one molecule of water. I. -2911 of substance gave--3818 of CO, and -0570 of H,O. PERKIN ON SOME NEW 11. *3850 of substance gave- 05010of CO, and -0787 of H,O. These give numbers agreeing with the formula -C,,H,,O,Ba”2 SO,H,O ae the following comparisons will show :-Theory. Experiment. c f A % I. 11. c,,.... 216 35.70 35-77 35.70 Hi,. .. 12 1-98 2.17 1-98 O,,.... 176 29.09 I -Ba .... 137 22-65 s .... 64 10.58 -605 1oo*oo Strontic Xulphocoumal.ilate.-This salt is easily soluble in water and crystallises very nicely. It contains water of crystallisation becoming opaque at 100” C.the last quantities of water not being expelled until a much higher temperature is used. A determination of the strontium in the anhydrous salt gave the following numbers :--1698 of substance gave- =0574of strontic sulphate = 16-15 per cent. strontium. The formula Cl,Hlo0,Sr”2S0 requiring 16.27 per cent. -0769 of a second specimen dried at about 110’ C. gave -0253 of strontic sulphate = 15.69 per cent. of strontium. The formula C,,HlO0,Sr”2SO, H,O requiring 15.75 per cent. Disulphocoumarilic Acid. On heating a mixture of about eight parts of fuming sul- phuric acid and one part of coiimarin to a temperature of 150” or 160’ C. for an hour or two the product contains two sulpho-acids viz.sulphocoumarilic and disulphocoumarilic acids. On treating this with baric carbonate in the usual manner the solution contains the barium salts of these two acids. To separate them the solution is evaporated to dryness and treated DERIVATIVES OF COUMARIN. with warm water which removes the baric sulphocoumarilate leaving the less soluble salt of the new acid behind. This is purified by crystallisation from boiling water in which it is not very soluble. Thus obtained it is a white slightly crystalline product nearly insoluble in cold water. Dried at 100’ C. it gave on analysis the following numbers :-03258of substance gave- 01648of baric sulphate = 29.76 per cent. of barium. The formula CSH,02Ba”2S0,,H,0 requires 29.85 per cent.of barium. Determinations of water of cry stallisation- I. 1.4226 of salt dried at 100’ C. lost 00486of H,O at 180’ C. = 3.42 per cent. 11. *5612of salt dried at 100”C. lost *0235of H,O at 180’ C. = 4.18 per cent. The above formula require8 3-92 per cent. Determination of barium in anhydrous salt- 01904of substance gave *0994 of baric snlphate = 30.7 per cent. The formula CSH,0,Ba”2S0 requires 31.06 per cent. From what has been said of the bromine and chlorine deriva- tives of coumarin it is evident that the bromine or chlorine introduced must be related to Merent carbon groups according as the product belongs to what has been termed the u or p derivative. In the case of the latter it is evident that it is contained in the C group as these bodies are produced from the brominated hydride of salicyl; those employed in this paper being represented thus :-Hydride of bromosalicyl.Hydride of dibromosalicyl. The bromine in the bromocoumarin obtained &omt)hese bodies by means of acetic anhydride is not attacked by boiling with potash. In the alpha series the bromine or chlorine must be connected VOL. XXIV. F PEREIN ON SOME NEW with the carbon of what may perhaps be called the acetic residue. These are easily decomposed with caustic alkali. I have endeavoured to produce a bromocournarin of this class by employing bromacetic anhydride instead of acetic an- hydride in the preparation of coumarin from the hydride of salicyl but have not yet succeeded. In OL dibromocouinarin one half of the bromine appears to be in union with the C group the other being connected with the acetic residue as only one atom of bromine is removed by boiling with potassic hydrate.a Bromo-and clilorocoumariiis from their decomposition by caustic alkali and production of couniarilic acid would appear to to be bromide and chloricl\ of :inacid radical (coumaryl). If it mere so however these substances should give with ammonia an amide which wodd decompose on boiling with alkali yielding ammonia and coumarilic acid ; but although the substances are easily acted upon by annionia the product when boiled with potassic hydrate does not yield this acid. It is therefore possible that coumarilic acid is not a true acid containing the group COHO but is only coumarin with one of hydrogen replaced by hydroxyl unless some molecukr change takes place during its formation ; and it i8 perliaps worth remarking that coumarin and its bromine chlorine and sulphuric derivatives give yellow solutions with caustic allrali whereas coumarilic acid forms colourless ones ;this may perhaps point to a change in struc- ture.I hope however to replace the hydroxyl in coumarilic acid by bromine and see if the resulting conipound is ordinary u bromocoumarin. Fittig and others consider coiimarin as the anhydride or glycollide of oxycinnamic rtcicl and it appeared to me probable that if it weie so it should yield nith phosphoric chloride the chloride of clilaocinnamyl. I have not however as yet suc- ceeded in obtaining this body clilorocoumarin being thc principal product found.I must say that if coumarin be a glycollide it is a very 8110-malous one in its properties as it may be kept d&sol& in caustic alkali for months without formation of any appreciable quantity of comnaric acid; neither does it form an arnidc when heated alone in gmeous ammonia or in a sealed tube Tvith alcoliolic ammonia ;whereas xalicylide the glycollicle of salicylic acid is converted into a salicylate as quickly as it dissolves in DERIVATIVES OF COUMARIN. an alkali and from the description given it would appear that it cannot exist in solution in alkali. Coumarilic acid differs in composition from coumaric acid by H, and from inelilotic and phloretic acids by H, so that we have the following series :-CgH,03 coumarilic.C,H,O coumaric. C9H,,0 melilotic and phloretic. These acids are however very different in properties for example phloretic and melil otic acids distil with formation of their anhydrides and couinarilic acid distils with only partial de- composition whereas the intermediate compound couniaric acid when heated forms a brown resinous mass and when distilled is entirely split LIP; if coumarin were its anhydride we should expect it to be produced especially as it is very stable and easily volatilized. The following is a list of the new products described in this paper :-Dibromide of coumariri .......... 'gH6 02,Hr2* Dichloride of coumarin .......... CgH60,Cl,.a. Bromocoumarin .............. CgH,BrO,. p. Bromocoumarin .............. C,H,BrO,. a. Chlorocoumarin .............. CgH5C10,. p. C~L lorocozcrnarin .............. C9H5Cl0 (Basecke). a. Dibromocoumarin ............ CgH,Br20,. ,8. Dibromocoumarin ........... C,H,Br,O,. Tetrschlor ocoumarin ............ CgH,C140,. Coumarilic acid ................ C,Hs03* Bromocoumarilic acid ............ CgH5Br0,. Sulphocoumarilic acid. ........... C,H602S0,. Disulphocoumarilic acid .......... C9H60,2S03.

ISSN:0368-1769    

DOI:10.1039/JS8712400037

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

ARMSTRONG ON THE ACTION OF SULPHURIC ACID V.-On the Action of XukT~uricAcid on the Natural Alkaloids By HENRYE. ARMSTRONG. THEexperiments the results of wliich are given in this paper form part of a series commenced in conjunction with the late lamented Dr. Matt hies s en. The action of sulphuric acid on the natural alkaloids was first made the subject of investigation by Arppe who in 1845 shortly described a body obtained from morphine to which he gave the for~i~la-4((C3,H,,N,06) + 550,. Ilaur ent and Gerhardt (Ann. Ch. Phys. [3] xxiv. 112) led by their researches on the Amides and Anilides to doubt the cor-rectness of this formula-which if true would imply that a reaction had taken place entirely without analogy-reinvesti- gated the matter further including both morphine and narcotine in their experiments.From the results obtained they con-sidered the cornposition of the bodies which they succeeded in preparing to be' represented by the f'ormuh C,,H,,N,O,S and c46H,,N,0,,S and termed them respectively suZp7iomorphide and suZphonamotide looking upon them as derived from the neutral sulphates of the bases by abstraction of the elements of 2 mols. OH, They considered them in fact to be true amides and as bearing the same relation to the neutral sulphates of the respective bases as sulphamide and snlphanilide bear to the neutral sulphates of ammonia and aniline. They were unable also to separate a base from the narcotine compound by the action of potash and this seems to have flirther strengthened them in t*heir opinion as to its constitution.By the action of sulpliuric acid on codeine they obtained a body identical with it in composition to which they gave the name of modified or amorphous codeine. The light thrown on the constitution of the organic bases by the researches of Dr. Matthiessen and others rendered it highly improbable that the above-mentioned bodies were con- stitutedas supposed by Laurent and Gerhardt and even allowed a speculation as to their probable nature for the dis- ON THE NATURAL ALKALOIDS. covery of apomorphine at once seemed to point to the possi- bility of the morphine product being none other than the sulphate of that base especially as the description of its pro- perties agreed moderately well with those characteristic of apomorphine.Their identity was proved by Drs. Matt hies sen and Wright! who succeeded in isolating npomorphine from the product of the reaction of dilute sulphuric acid on morpliiue in sealed tubes at looo. This rendered an analogous constitu- tion of the narcotine and codeine products probable a surmise which has however not been confirmed by experiment. On heating narcotine with an excess of acid of the strength of equal volumes of ordinary concentrated sulphuric acid and water in an open porcelain dish on a water-bath it is observed that the colour of the mass gradually darkens and that after a time and almost suddenly the whole becomes of a dark pink colour. It is t,lien thrown into a considerable quantity of warm water in which it entirely dissolves and a slight excess of ammonia is added which throws down the base as an amor-phous almost white precipitate.This was brought on a filter and washed with warm water. It was found to be very easily soluble in alcohol insoluble iii carbonate of soda readily soluble in potash and when heated under water to cake together in the form of a sticky semi-fluid mass. This behaviour at once Buggested the probable nature of the base; for all the above properties agree with those exhibited by the first product of the action on narcotine viz. dimethylnornarcotine ; and a further examination soon proved this to be really tlie case. The product was purified by solution in hydrochloric acid; addition of sodic carbonate in excess to remove any monome- thylnornarcotine which is soluble in the latter reagent ; redis-solution in hydrochloric acid ; and addition of potash in excess which dissolves dimethylnornarcotine leaving any nornarcotine or narcotine undissolved.The alkaline solution was then neutralised with hydrochloric acid and ammonia was added ; the base so obtained and dissolved in hydrochloric acid preci- pitated by sodic carbonate was extracted with ether ;the ether sliaken up with hydrochloric acid ; the hydrochloric acid solu- tion precipitated with ammonia; and the base after washing dried at 100' and analysed. 1. *4917 grm. gave -2332 grrn. OH and 1.1397 grm. CO,. 2. 0366grm. gave ,1724 grm. OH and 08455 grm. CO,. 58 ARMSTRONG ON THE ACTION OF SULPHURIC ACID Calculated.Found. v-/-I. 11. c, ..... 252 63.1G 63.2 63.1 H, ...... 21 5.26 5.2 5-24 N.. ...... 14 3-51 -0 ...... 112 2S.07 -C,,H,,N@ 399 100*00 The above aiinlyses prove beyond doubt the identity of the base with dime tli yhor :I m a 0 tine. The conversioii of the nnrcotine was pcrfect and if the reaction M as arrested immediately 011 the appearance of the pink coiour throughout tlie ~lde aii almost pure product iiic~xs was obtained as is shown by tlie following aiialj-sis of the crude product obtained by rlii*ectly precipitating tlie base with ammonia and washing ivith warm water :--54 grrn. gave -265 grm. OH and 1.247 grm. CO,; whence C = 63.0 per cent. H = 5.4 per cent. Tlie reaction has therefore taken place according to the equation :-C,,H,,NO + H,SO = C,,H,,NO + CH,HSO,.The methylsulphoviiiic acid formed is again decomposed into sulphuric acid and methyl alcohol for on adding bark carbonate in cxcesx filtering and evaporating to dryness no baryta salt wits obtaincd. For the complete conversion of 50 grms. narcotiue I have found it necessary to heat between two and three hours. If the heating be continned beyond the above-mentioned point a second atom of methyl can be removed arid probably a third; but a very impure product is obtained sulphurous anhydride is given off and partial carbonisation takes place. By the analysis of a crude product obtained by further heat- ing &c. the following results were obtained :-,4125 grrn.gave -1945 grm. OH aid *937 grm. CO,; there-fore C = 61.9 per cent.; H = 5.2 per cent. It is probable that the substance analysed by Laurent and Gerhardt was a mixture of the sulpliates of di- and mono-metliylnornarcotine. That they should have been led to consider it an arnide and not the sulpliate of a base evi- ON THE NATURAL ALKALOIDS. 59 dently arises fi-om the fact that dinietlilvliioriiarcotine is soluble in potash and that on the addition of an acid the respective salt is precipitated and only dissolved again on addition of a large quantity of water. On treating their product with nitric acid they obtained a yellow substance soluble in ammonia andbf course were able to detect sulphiiric acid in the solu- tion whereas if the pure substance prepared as above is similarly treated the yellow body is obtained which is per- haps a nitro substitution product but not a trace of sulphuric acid can be detectcd.On treating codeine in a similar manner and heating until the precipitate produced by sodic carbonate did not visibly increase; then dissolving the product in water) precipitating with sodic carbonate redissolving in hydrochloric acid and repre- cipitating with sodic carbonate which operation was twice re- peated in order to remove any codeine,-then extracting with ether and shaking up the ether with concentrated hydrochloric acid a crystalline hydrochlorate was obtained which on analysis gave numbers agreeing very well with those calcu- lated for hydrochlorate of codeirie.I. *517grm. gave 0309 grm. OH + 1.2162 grm. CO,. 11. -5725 grrn. , *3423grm. OH + 1.3558 grm. CO,. 111. -2257 grm. , -0905 grm. AgC1. Calculated. Found. I 7-I. 11. 111. c, .... 216 64-38 64-15 64-58 -H, .... 22 6.26 6.64 6-64 -NO .... 62 --I c1 ... . 35.5 10.5 -10.4 A platinum salt was prepared and analysed with like result. 0552grm. gave *lo67Pt = 19-32 per cent. Pt. BC,,H,,NO,HCl,PtCl requires 19.5 per cent. The first product of the action of sulp1iur.k acid on codeine is therefore a body isomeric therewith. 11s properties are as follows :-The base fhlls down as a snow-white amorphous precipitate on the addition of sodic carbonate. (Codeine is only precipitated after some time from concentrated solutions and always crystalline.) The hydrochlorate crystallises in groups 60 ARJTSTRONG ON THE ACTION OF SULPHURIC ACID ETC.of apparently hexagonal pyramids radiating from a common centre and differs from the corresponding codeine hydrochlo- rate by losing both its molecules of water of crystallisation at loo",whereas the former loses only 4 at loo" the remaining only being expelled at 120". The platinum salt is quite amorphous and may be obtained anhydrous by drying at loo" whereas the platinum salt of codeine is crystalline and does not lose the whole of its water of crystallisation below 100". The amor- phous platinum salt contains 1mol. water of crystallisation which it loses even by prolonged exposure over sulphuric acid. Gerhardt's description of the base &c.differs from mine iriasmuch as he says that not only the base but all its salts are amorphous. By the further action of sulphuric acid I have evidence that first 1mol. OH is removed from '2 mols. of codeine an inter- mediate compound between codeine and apocodeine being produced a sort of anhydride in fact; and then 1mol. OH from 1mol. codeine; and I believe that by its flirther action on this apocodeine apomorphine is formed i.e. CH is removed. I am however not yet certain as to the exact conditions under which the first of these changes takes place and the products being amorphous it is extremely difficult to obtain a satisfactory separation. With regard to morphine I have as yet unfortunately not had sufEcient quantities of material to work on to enable me to speak with certainty but I think it probable that it is first converted into such an isomeric modification as codeine and that also intermediate compound exists between it and apomorphine and derived by abstraction of OH from 2 mols.of mor-phine. By the action of sulphuric acid on other bases I have ob-tained entirely negative results ; neither strychnine nor Papa-verine is 111 the least affected by it even after many hours' digestion. It will be interesting to extend the investigation to those alkaloids known to contain the methyl group such as brucine and caffeine ;and with these I have already commenced experi- ments. PAGES ARE MISSING FROM 61 TO 84

ISSN:0368-1769    

DOI:10.1039/JS8712400056

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

P t 26.76. VI.-Ow M L Alknloi’d from Chtchona Bark hitherto Undescribed. results :- 7 Pt. ‘r 26.63 26.62 Gerhardt’s formula for the anhydrous platino-chloride of quinine C,,,H,N,O2 2HC1 PtCll requires H 3.53 The salt taken for analysis was precipitated from a hot acid solution and was a distinctly crystalline powder. The composition is the same whether it be precipitated cold in a By DAVID HOWARD. IN experimenting upon impure crystallisations of quinine salts obtained from the mother-liquors of the manufacture of sulphate of quinine I have occasionally been perplexed by an unusual loss in recrystallising which the mechanically adhering mother-liquor did not seem to account for. A more careful examination of some of these substances shows that the cause in some cases at least is the presence of an alkaloid hitherto undescribed the extreme solubility of the salts of which both dis- tinguishes it at once from the cinchona alkaloids already known and renders it very difficult to separate from the uncq-stallisable quino’idine.The most convenient method of obtaining it is to purify the alkaloids contained in the mother-liquor from the recrystallisation of such impure products as I have mentioned by solution in ether and after evapora- tion of the ether to dissolre with oxalic acid in as small a quantity of water as possible and allow it to crystallise. The oxalate thus obtained may be purified by recrystallisation from water with addition of animal charcoal but I have never been able to free it entirely from a yellow colour.The most satisfactory salt for analysis is the platino-chloride which is prepared in the usual manner ; it is almost insoluble in water or in cold hydrochloric acid but soluble with difficulty in hot strong acid; it forms a crystalline powder by precipitation ancl well defined crystals by solution in acid. The analysis shows that it is isomeric with the platino-chloride of quinine but anhydrous instead of containing one atom of water of crystallisation given off a t 120” as does the salt of quinine. The ultimate analysis for which as well as for the other combustions which I shall have to mention I am indebted to the skill of Mr. Huxley and Mr. Gray of the Royal College of Chemistry gives the following Experiment I .. . . . 32.67 H. 3.67 3.82 C. I1 32.67 C 32.60 G VOL. XSIV. neutral solution or crystallised from a strong acid solution as the fol- lowing results will show :- do Platino-chloride precipitated cold Pt 26.50 crystallised 26.68 ' The oxalate as I have before mentioned though it is the most easily ci-ystnllised of the salts of this alkaloid is unfortunately very difficult to purify entirely and changes so readily under the influence of air light or heat that I hare been unable to obtain it colourless. When a dilute aqueous solution is concentrated by evaporation in a mater-bath tlie change of colour sliows that decomposition has to a certain extent taken place and on the addition of water a brown resinoid matter sep:wates from tlie solution.To find out if this was caused by im- puriries or was a property of the salt itself I decomposed the platino- cliloride of known purity by several processes but iu each case the resulting oxalate had the same colonr and the same tendency to decom- pose. Even when prepared from perfectly colourless solutions of the dlrnloicl in ether I hare still found the oxalate of a greenish-yellow hue even before the application of heat ; in fact I am not sure that this colour may not be inherent in tlie salt itself. I t is exttemrly soluble in water tlie wet crystals melting a t loo" but inucli less so in cold water ; insoluble in ether but very soluble in alcoliol ancl to a less degree in amylic alcohol from hot concentrated solutions in either of which menstrua it crystallises freely on cooling.The water of crystallisation is partially given off in vacuo and entirely a t 100" after previous drying; if the salt is at once heated to 100" witliout prcvious exsiccation it is apt to fuse. The conibnstion proved exceedingly difficult ; the usiial process with cupric oxide was found inadmissible the oxalate assuming a dark brown colour as soon as it touchcd the oxide. The only practicable method is buriiiag in oxygen gas ancl even in this mode of analysis the low temperature at wliich tlie substance partially decomposes makes it diflioult to accomplish successfully. It will be seen that the results though agrceing very closely among themselves differ considerably from tlie probable formula showing plainly the difficulty of obtaining a purc product.The hydration and the oxalic acid point to the formula 2(C,,H,,N,O,),C,H,O + Saq. thc numbers obtained being :- H. 7.55 8.64 8 . i 4 C . Theory . . 56.00 Exp. I . 57'57 , 11 57.42 , 111. 57.74 , IV . 5i.85 9.14 8.79 CSHLOI. HLO at 100. 1 1 2 0 in vacuo. 14.23 14.09 10.00 10.07 9.98 10.08 18'00 17.98 17.98 17.89 l i . 7 2 14.02 13.82 10.23 10.19 17.98 - - 7 ) v * - - HITHERTO UNDESCRIBED. G3 The water lost by drying in racuo agrees very closely with 7 atoms viz. 14.00 per cent. ‘Ihe salt thus differs from oxalate of quinine by 3 atoms of watcr of crystallisation the foi-mula of the latter being 2( C,oH,,N,Oz),CzH,O~ + 6aq.The properties of the other salt,swhich I have examincd arc as follows :-The sulphate tartrate citrate hydrochlorate phosphate and acetate are all exceedingly soluble in water ; on evaporation in vacuo they form semi-crystalline masses impossible t o obtain in a state fit for analysis. The hydrobromate and ferrocpnide obtained by double decomposi- tion form oily strata a t the bottom of the solution solnblc in an additional quantity of water but eren on long stancling thcy show no sign of crystallisation. The hydriodate also forms an oily stratum in strong solutions but on standing it becomes semi-solid by the formation of crystals ; n-eaker solutions also deposit a small quantity of flocculent crystals but in neither case can they be separated from the mother-liquor.The sulphocynuide while also forming an oil when in concentrated solutions crystallises from a somewhat larger quantity of water in long silky needles almost white rery soluble and readily decomposcd by hcat. The iodo-sulphate I have not as yet succeeded in forming. I much regret this on account of the great importance of this salt in the cin- chona alkaloids and further experiments are needed either to form it or t o prove its absence. The alkaloid itself as obtained by precipitation from a solution of its salts by potash o r soda is a yellowish oil. I have not bcen able to obtain it pure in the solid state for it mill not bear heat without decorn- position and holds water too strongly to dry in vacuo. It is very soluble in alcohol soluble to a large extent in ether from which it separates as an oil when the ether is allowed to evaporate.It is B strong base ; the salts are neutral to test-paper ; a small exccss of the base strongly restores the colour of reddened litmus. Ammonia pre- cipitates its solutions but imperfectly and if we may judge from this it is even a stronger base than quinine. Chlorine-~vater follond by ammonia produces in solutions of its salts the green colour and precipitate of dalleiochin which distinguishes quinine and quinidine. Strong acids even in the cold produce a change of colour and even Tvhen dilutcd with a considerable quantity of water ; heat renders the action much more rapid. This coloration is strongest when nitric acid is used an excess of which with the aid of heat will develope a strong yellow-green colour even in a meak solution.In this reaction as well as in the persistent colour of its salts this alkalo’id shows a curious resemblance to aricine. G 2 EKIN ON THE ORIGIN OF NITRATES i ' 1 VII.-Ou the O,?giiz of Ai'trates in Potable TVizfers. By CIIARLES EPIS Batli. 64 The yellow colour renders the examination of its optical properties difficult but as far as has been hitherto tried it is inactive. I hare not been able to recognize fluorescence in its solutions. Its taste is a pcculiar bitter very much less both in intensity and permanence tlinii that of the other cinchona alkaloids. I have not been able to find out whether this alkaloid is contained in all the species of cinchona or if not to which it belongs for the diffi- culty of tlie crystallisation of the impure salts makes it a matter of uncertainty to obtain it.My unclc Mi-. J. E. Howard when investigating the leaves of the Ciiicliom Siccci~nLhmc from India found minute quantities of an alka- loid soluble in ether froni which an alcoholic solution of oxalic acid precipitated i t in a crj-stalline form ; bat the small quantities a t liis disposal prerented his examining it further than to show its analogy 7Vith quinine ; his present conviction is that this substance is identical with the alkaloid I hare been describing and though the eviclencc is not yet sufficient to cnable us to speak with certainty it teiids strongly to prove it. It seemed so desirable t o settle this point and to tlirom some light if possible on the order of formation and possibly on the fnr more important and far more difficult question of the mode of forniation of the alkaloids of the descending sap that he has written to Mr.Broughton and we hope shortly to receive a quantity of the leaves sufficient to enable us to investigate it. I DAVE frequently been a t a loss to account for the presence of con- sidcrable quantities of nitric acid in potable waters where contamina- tion by sewage or manured land was out of the question. To give but ono instance tlicre is a hill near Bath capped by the Great Oolite which has not a siiigle house upon it no drainage near it and on n-hose scanty herbage browse oiily a few sheep and yet the springs rising a t tlie junction of tlie Oolite with the Fuller's earth contain as much as . r j j grains of nitric acid per gallon. Here then after making all due allom- ance for the combinecl nitrogen contained in rain water which according to tlie observations of Lawes Gilbcrt and Way amounts to .?+k parts nitrogen in l,OOO,OUO tliere still remains the large proportion of eight to one to be accounted for. And this proportion will be still further increased if we consider that much of the nitric acid and ammonia

ISSN:0368-1769    

DOI:10.1039/JS8712400061

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

EKIN ON THE ORIGIN OF NITRATES i ' 1 VII.-Ou the O,?giiz of Ai'trates in Potable TVizfers. By CIIARLES EPIS Batli. 64 The yellow colour renders the examination of its optical properties difficult but as far as has been hitherto tried it is inactive. I hare not been able to recognize fluorescence in its solutions. Its taste is a pcculiar bitter very much less both in intensity and permanence tlinii that of the other cinchona alkaloids. I have not been able to find out whether this alkaloid is contained in all the species of cinchona or if not to which it belongs for the diffi- culty of tlie crystallisation of the impure salts makes it a matter of uncertainty to obtain it. My unclc Mi-. J. E. Howard when investigating the leaves of the Ciiicliom Siccci~nLhmc from India found minute quantities of an alka- loid soluble in ether froni which an alcoholic solution of oxalic acid precipitated i t in a crj-stalline form ; bat the small quantities a t liis disposal prerented his examining it further than to show its analogy 7Vith quinine ; his present conviction is that this substance is identical with the alkaloid I hare been describing and though the eviclencc is not yet sufficient to cnable us to speak with certainty it teiids strongly to prove it.It seemed so desirable t o settle this point and to tlirom some light if possible on the order of formation and possibly on the fnr more important and far more difficult question of the mode of forniation of the alkaloids of the descending sap that he has written to Mr.Broughton and we hope shortly to receive a quantity of the leaves sufficient to enable us to investigate it. I DAVE frequently been a t a loss to account for the presence of con- sidcrable quantities of nitric acid in potable waters where contamina- tion by sewage or manured land was out of the question. To give but ono instance tlicre is a hill near Bath capped by the Great Oolite which has not a siiigle house upon it no drainage near it and on n-hose scanty herbage browse oiily a few sheep and yet the springs rising a t tlie junction of tlie Oolite with the Fuller's earth contain as much as . r j j grains of nitric acid per gallon. Here then after making all due allom- ance for the combinecl nitrogen contained in rain water which according to tlie observations of Lawes Gilbcrt and Way amounts to .?+k parts nitrogen in l,OOO,OUO tliere still remains the large proportion of eight to one to be accounted for.And this proportion will be still further increased if we consider that much of the nitric acid and ammonia IN POTABLE WATERS. 65 present in rain mater must be absorbed by vegetation in its passage through the soil. It has of course long been known that water from artesian wells in the chalk contains nitrates which cannot possibly bc refcrred to sen-ago or other impurity but I am not aware that it has becn suspcctcd that other strata might also contain nitrates. It was to ascertain this in the absence so far as I know of any publishcd expcrimcnt bcaring on the subject that the following experiments mere macle and t o ascer- tain if possible the origin of these nitrates which according to Dr.Paul in his comprehensive article on Water Analysis in m a t t s ’ s Dictionary of Chcmistry has not yet been done. The rocks and fossils mentioned below wcrc all most carefully col- lected by myself from situations There any accidental containine tion seemed impossible none of them having been exposed to tlie mcatlier or to percolating impurity. The method I pnrsued was to p o w h the fossils rougllly a i d macerate themfor a few days in perfectly pure clistillcd water; to pour off thc clear supernatant liquid ; add an eclnal rlumtity of solution of pure sodiiun hydrate (1 to 10) ; transfer to a retort; clissolvc in tlic liquid a piece of thin sheet aluinininm ; collect the ammonia by distilla- tion; ancl estimate it by Ncssler’s test.The utmost care was used to insure the purity of tlie mater ancl solu- tion of sodium hydmte and perfectly negztive rcsults werc obtained i n each case by blank experiments. Procecding in this ay I found that grey chalk marl contained 1.1 part of combined nitrogen in 1,000,000 parts ; Bath oolite 1.3 parts ; fossils from the Green-sand 2.23 parts ; fossils from tlic Lias 3.6 parts ; another sample of fossils from the Lias Ji parts ; fossils from tlic Fuller’s earth newly 3 parts j a seinplc of Inferior Oolite rock i . 6 parts ; and another sample of the same 6 9 parts. The samples of Iiifcrior Oolitc rock were entirely made up of fossils and although I hail erery rcason t o trust the results given by my first experiment yet thc quantity of nitrogen present mas so high that J obtained the second snmplc fiom :L different locality but it gave almost the same results.Tlic high figure of combined nitrogen given by tho Inferior Oolite canscd me t o look a t my note-book ancl I found that almost without exception the springs in this neighbourhood mliich I hare examined and wliicli had pcrco- latcd through the Inferior Oolite rising a t its junction with thc Lias contained a larger quantity of nitric acid varying from 14 p a i n to 2 grains per gallon than the springs rising a t the junction of‘ tlic Cheat Oolite with the Fuller’s earth and this I attribute to thc onc stratuni being so much m7re fossiliferous than the other.It is still the practice of many of our first analysts to look with great suspicion upon maters containing any appreciable amount of nitric acid FRANKLAND ON THE DEVELOPMENT OF FUNGI VIII.-OIP tlLe Development of FumgSi in Potable Water. By E. PRANKLAND Ph.D. D.C.L. P.R.S. 66 bat that this nitric acid is not necessarily due to tlie oxidation of excretal matter I think the foregoing experiments sufficiently prove and I ven- ture to think in consequence that the “ previous sewage contamination theory” ought to be considerably modified. IN June 1870 Mr. ITeiscli communicated to the Chemical Society the results of some rery interesting obserrations on the derelopment of cellular and fungoid growths in various waters to which a small quantity of crybtalliiie s u p - liad been added.Having observed this phenomcnon in water to wliich sewage was strongly suspected to have gained access lie procured water from various sewers and after allom- ing the suspended ma,tters to settle six drops of each sample of clarified liquid were mixed with 10,000 grains of West Middlesex and New Rivcr water and to G oz. of each sample thus polluted 10 grains of pure sugar were added n like quantity being mixed with cj oz. of the watcr without tlic sewage. All the samples were placed in stoppered bottles in a window where plenty of liglit could reach tliem. It was founcl tliat the watcr and sugw reinained clear and sweet as did also lhe water and sewage vithout sugar ; but the mixtures of water sewngc and sugar became turbid and on being submitted to microscopic examination were found to contain small spherical cells nith in most cases a very briglit nucleus.After the lapse of some days these cells gradually grouped themselves together in bunches something like grapes ; t,liey next spread out into strings with a wall surrounding and connecting the cells ; the original cell-walls then seemed to break and leave apparently tubular sort of threads branched together. A h . Heisch then describes a number of other experiments which taken together with tlic foregoing led him to tlie conclusion that the cells of these germs whcn thus dex eloped are distinct evidence of sewage contami- nation and that the germs producing tliese cells are not removed by filtration through the finest Swedish paper neither are they destroyed by boiling for half-an- hour. These remarkable results excited in myself and doubtless in other cheinists occupied in the inrestigntion of potable waters the liveliest intercst. h i comeetion with the most generally accepted hypothesis of the cause of the spread of epidemic disease tlirough the agency of water there was liere discovered a much nearer approach to the supposed iiiorbific matter in such water than had before been attained. Another parallel mas apparently opened from which one of the strongholds of

ISSN:0368-1769    

DOI:10.1039/JS8712400064

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

FRANKLAND ON THE DEVELOPMENT OF FUNGI 66 bat that this nitric acid is not necessarily due to tlie oxidation of excretal matter I think the foregoing experiments sufficiently prove and I ven- ture to think in consequence that the “ previous sewage contamination theory” ought to be considerably modified. VIII.-OIP tlLe Development of FumgSi in Potable Water. By E. PRANKLAND Ph.D. D.C.L. P.R.S. IN June 1870 Mr. ITeiscli communicated to the Chemical Society the results of some rery interesting obserrations on the derelopment of cellular and fungoid growths in various waters to which a small quantity of crybtalliiie s u p - liad been added. Having observed this phenomcnon in water to wliich sewage was strongly suspected to have gained access lie procured water from various sewers and after allom- ing the suspended ma,tters to settle six drops of each sample of clarified liquid were mixed with 10,000 grains of West Middlesex and New Rivcr water and to G oz.of each sample thus polluted 10 grains of pure sugar were added n like quantity being mixed with cj oz. of the watcr without tlic sewage. All the samples were placed in stoppered bottles in a window where plenty of liglit could reach tliem. It was founcl tliat the watcr and sugw reinained clear and sweet as did also lhe water and sewage vithout sugar ; but the mixtures of water sewngc and sugar became turbid and on being submitted to microscopic examination were found to contain small spherical cells nith in most cases a very briglit nucleus. After the lapse of some days these cells gradually grouped themselves together in bunches something like grapes ; t,liey next spread out into strings with a wall surrounding and connecting the cells ; the original cell-walls then seemed to break and leave apparently tubular sort of threads branched together.A h . Heisch then describes a number of other experiments which taken together with tlic foregoing led him to tlie conclusion that the cells of these germs whcn thus dex eloped are distinct evidence of sewage contami- nation and that the germs producing tliese cells are not removed by filtration through the finest Swedish paper neither are they destroyed by boiling for half-an- hour. These remarkable results excited in myself and doubtless in other cheinists occupied in the inrestigntion of potable waters the liveliest intercst.h i comeetion with the most generally accepted hypothesis of the cause of the spread of epidemic disease tlirough the agency of water there was liere discovered a much nearer approach to the supposed iiiorbific matter in such water than had before been attained. Another parallel mas apparently opened from which one of the strongholds of 67 IN POTABLE WATER. disease could be a t least reconnoitred if not actually attacked and vanquished. At the earliest possible moment I repeated and extentlcd these cx- periments and a t the outset had the advantage of seeing in Xr. Heisch’s laboratory the cells and fungold growth which lie clcscribcd in the papei- already alluded to. At a subsequent stage of my inquiry I was also much indebted to Mr.Bell of the Inland Revenue labora- tory for information about and specimens of rarious fungoid growths some of which are alluded to in his Faluable paper on “ Fungi and Fer- mentation,” recently published in the Journal of the Chemical Socicty. My own experiments completely coiihm Mr. Heis ch’s obserrations with two important exceptions T-~z. that firstly the fungoid growths are not peculiar t o water contaminated with sewage ; and secondly the germs from which they originate are present in all water 1~111cll has been even momentarily in contact with thc air. Samplcs of xLtm which when mixed with the proportion of sugar wluch he rcco~nmc~ids remained clear and transparent for n eeks rapidly became tnrbicl wllcn a few drops of sewage were added to them; and the consecutive dc- velopment of clusters of cells and threads occurred cxactly as 11e describes.One drop of fi.esli urine in 10,000 grs. of water soon pro- duced crowds of cells and at a later period mycelial threads. Samplcs of effluent water from meadows irrigated with sewage wlicn mixed with sugar presented perfectly similar phenomena as clid a150 samples of well mater yielding the following results on analysis p Besults f Annlysis eqiraa.wd in p r t s p e r 100,000. Gultan’s Row Well > E 2 n - Tellow C l C U . Sliglitly tu I-bid . I Orcliard water; 8 mouth thorue Ea4 ft. Retfoi-d . tow 5 West \Vcll ft. deep . depth Ynr- Cra- to i Jacob’s field .Well Shef- 1 Offcnsir s nivnrnriiig wirli vilirios i l l l d bnctcria. Very turbid. Pump in Sheep Street Ciruncesler - FRANKLAND ON THE DEVELOPMENT OF FUNGI 68 Samples of water taken from the Thames above Streetley and below Reading and from the Kennet below Reading also gave under the same conditions fine mycelial growths. On the other hand the water delivered by the eight London Water Companies gave in but one or two cases slight evidence of cellular or mycelial development whilst the following samples exhibited even after several weeks' contact with sugar no signs of the characteristic cells and fungi nor indeed of any other organisms :- 4 e - 0 '001 ,004 '118 IZe.sults qf Analysis expressed i i L p a r t s p e r 100,000..- B d 1-1- 11'94 0 100.88 '059 deep furnisliihg Harrow Head > Shallow Harrow Well Hill near . top of 1 63'92 '078 Well in chalk. 310 feel) Deep chalk well water at Canterbury softened by Clark's process _. Cerney Springs Tlianies I 33'86 .052 water supply . _. . . . . 1 Hardness. ' 0 0 G 0 '001 Water from bore Iiolc in nasliey Meadows near ' 33'88 ,027 Watford 130feet&vp . Clialk ivell 378 feet deep 29.20 '05? 23.30 '081 - Thus far my results were quite in harmony with those of air. -Heisch and in accordance with what might be anticipated from a knowledge of the sources of the waters and of their previous history as revealcc1 by chemical analysis ; but I nom encountered some reactions which at first puzzled me exceedingly.The first of these was the following :- During a visit to hIr. Hope's new irrigation farm a t Romford on the 25th of November last I collected a smnple of effluent mater from one of tlic drain outfalls. This mater consisted of the sewage of Rom- forcl nhicli lind percolated to the tile drains through some four or fire feet of loose graTelly soil. It was clear but that it still contained a considerable proportion of unosidized sewage mas evident from the Eollowing results which it yielded on analysis- - I i B __ 0 ." z z 8 G -__ 2'10 1'30 22'76 6'30 18.98 1'35 23.71 1'18 21.91 h % .-. - 1 P ." - e 6 a Y - B '438 '299 .087 '127 '325 '083 ,123 ~ - '69 4'17 4'86 Clear.3'88 26'64 8'90 10.37 11.78 32'15 Clear. !8.42 4440 Clear. 3.77 2'1.04 Clear. 3'51 25'42 Clear. 1'00 16'41 3'73 19'14 Clear. IN POTABLE WATER. GD 100,000 parts contained :- Total solid inipurity in solution SS'G0 Organic nitrogen Nitrogen as nitrates and nitrites 1.143 Total combined nitrogen. . 1.419 '933 Organic carbon *844 Ammonia $040 Temporary hardness. . 27.95 Chlorine 8.30 Permanent , 20'GO , 48.S The proportion of organic caiboii mas thrcc times and that of organic nitrogen ten times as great as that found in nnpolluted -ater whilst the comparatively large propor'ion of ainmonin showed that ihc oxidation of the organic matters was still incomplete.Nercrtheless this water when mixed >j-ith the proper proportion of sugar and maintained at a temperature of about 70" Fahr. remainccl perfcctly transparent for weeks The result of the next expeibnent was still morc remmlxable. Two samples of the Grand Junction Company's wntcr wcre mixed with sugar in the usual way ; one of them was drawn from a € 0 ~ 1 nncovcred cistern over and within a water-cloFet ; the othcr from a clcan slatc cistern in passing out of which the water filtcred through some 30 or 40 lbs. of animal charcoal. The x d e r from the foul cistern remaincd transparent for weeks whilst that cli am-n from the clcan cistern through animal charcoal soon became turbid ancl in three dnxs hac1 prodnccd abundant fungoid growths.Reme mbcring Ah. H c i s cli' s statement that filtration through well nimtl animal cliarcoal is effcctnal in pre- venting these growths eren in foul water I nom p a y d n rapid cur- rent of air through the filter for :%bout 1.5 minutes ancl tlitn left it exposed to air for six hours. The result honrwer waq the fiame as before Grand Junction water drawn through it immcdiately after akation behaved exactly as before when niisecl mith sugar. Thcsc experiments seemed to indicate that the presence of a phosphate was in some way connected with the production of thc fungod growths end other living organisms ; for it is lmomn that mntcr dissolrcs traces of calcic phosphate from animal charcoal ancl this supposition mas strengthened Then it was found that the effluent n-atcr from the sewage farm a t Romford contained no detectable trace of pliosphoric acid tlie plants ancl poor soil of this newly cultivated farm 1iaTing cloulitlcss rc- moved all phosphates from the percolating sewage.Thc hypotli the dependence of the fungoid ancl otlier growths upon the presence of phosphates was further supported by the rcsults of thc following - - - .-._- FRANIiLAh‘D ON THE DEVELOPMENT O F FUNGI 70 1. A sample of the Grand Junction Company’s water mixed with mgar remained perfectly clear for twelre days ; minute quailtities of animonic nitrate and phosphate were now added. Three clap later it swarmed with very active vibisios and cells with bright nuclei sobse- qiiciilly very luxuriant brauchcd fungoid threads developed themselves and the mixture emitted a strong ferment odour which a few days later became Iiorribly offensive.2. A sample of the Southwark Company’s water mixed with sugar remained f o r 19 days perfectly clcar and transparent ; small quantities of amlnoiiic nitrate and p1ior:phate were then added. In a few days it was crowded with vibrios and inoiinds ; and later it was found to con- tain tlie charactcristic mycelid fibres. 3. The usual proportion of supr was added t o a snmplc of mater which I collected at the Cerney Springs near Cirencester ; it remailled clear for eigllt days and was then &xed with traces of arnmonic nit1 ate and sodic pliospliate ; it continued turbid erer afternards and soon bccaiiic fi lled wich snmms of yibrios and fine branching tubular fungoid threads ; tlie water subscquently became brownish and emitted D Yery offciisive odour.Il’hese experiments shorn that potable watcrs which stand the sugar test pcrfectly becuine entirely changed in their behaviour with this test ~ ~ l i c i i they are niixed witli ti-aces of ammonic nitrate and Bodic phosphate and the following experiments prove that it is the phosphoric salt which altcrs their beliavionr in this respect. 4. A sample of the Lumbeth Cornpanj’s water after admixture with sngnr rcnmincd perfectly c1e;u. for 19 clays ; aminonic nitrate i m s then d d c d ; after tlic lapse of several weeks the clearness of the sample hnd not been distubecl. 5. Canterbury deep wellxater softeiiedby C l a r k ’ s process remained perfectly clcar during 23 days after admixture with sugar ; traces of nitrate of aiiimonia were then added but after the lapse of two months it was still perfectly trauspareut and unchanged.6. A sample of tlie New Rivcr Company’s water after bcing mixed \vith sugar remained perfectly clcar for 19 daFs ; amnionic nitrate was then added but during a further perioll of 12 days no change took place. 7. The water of the shallow well at Harrow above alluded t o (p. 68) mixed with sugar and remained perfectly clear during 29 days ; one drop of a fresh solution of albumin was then added to about 1) ounce of it. Iu four days it became very turbid aud under the micro- scope showed bpleiidid branchtd tubular fungold threads filled with roulldcd cells pnd closely resembling those developed in mater with mhich sewage had been intentitrnally mixed.Cells with bright nuclei grouped together were seen in abundance together with leptothrix IN POTABLE M'ATER. 71 filaments. The solution of albumin used in this and other cxpcri- ments was made by breaking open a fresh egg and rapidly trniisfei,~~ing the white to a bottle containing about 6 oz. of pnre distillcd water which had been previously boiled for an hour a i d a half. Analysis proved this solution to contain distinct traces of phosphoric acid. 8. A sample of the Grand Junction Company's watcr softencd by Clark's process was mixed with sugar and remained clear during 19 days ; ammonic nitrate was then adclcd b u t no alteration occurrccl during the next six days.When however a few rcry minute frngmcnts of fresh animal charcoal were put into the water i t soon became turbid and exhibited under the microscope groups of cclls \rith bright nuclci and magnificent mycelial threads. It is thus evident that the addition of minute traces of n pliospl~ntc either as sodic phosphate? whit,e 0 egg or animal cllnrcod at. oncc determines these fungoid growt'hs in saccliarinc i n t e r wliicli b2for.c exhibited no tendency t o develop them. An important qucstion now presented itself Are the gcrnis of tlicse organisms nccessarily contaiiiecl only in tlie maters wliicli dovclop fungoid growths or are they present in tlie atmosplicre ? The aiiswer. t o this question was given by the following expcriment :- 9.Small quantities of potassic chloride ammonic nitratc sodic yhosphat,e and sugar were clissolvcd in distillcd wntcr prcviously boiled for many hours with caustic socla and potassic pcrmangnn:rtc and afterwards again distilled. Just. before solution tlie solid ingrc- dients were strongly lieated in a platinum spoon over tho flarnc of a spirit lamp-the potassic cliloride a d sodic pliosphate t o rcdncss tlic ammonic nitrate until a considerable proportion had decomposed into nitrous oxide and water and the sugar until aftcr melting it bcg:m to turn brown. This solution was placed in a stoppered bottle ns in :ill the previous experiments. After a few days' exposure to n. tcmpcra- ture varying between 60" and 70' I?.a magnificent mycelium of t,he characteristic description began t o OW and was soon followed by several others. Under the microscope the tlireacls of tliis fungiis wcrc uniformly tubular branched Tvit~h si~arsely-distributetl cclls inside and a few bulbs. There were also interspersed amongst the m p l i n m abundance of cells wit.h bright nuclei groupcd togcther like bunches of grapes. The liquid W ~ S also crowded with rery minute moring organisms probably monads. A specimcn of real sewcr fungus \vas examined side by side with this and found to bc rcry similar in ap- pearance but more transparent aud somcwliat smallcr. It is thus evident that the purest water wliicli can be obtnincd in contact with the air yields splendid crops of this sewngc mycelimn if it be supplied with the necessary soil ; and further that tlie sugar ancl salts just named contain all the elements necessary f o r its dcvclopmcnt.FRANKLAND ON THE DEVELOPAIEST O F FUKGI 72 Of these elements phosphorus is essential for in a solution made at the samc time exposed t o the same conditions ancl containing the same substances mii~iis f h c sotlr'c 217io~p7inte no trace of mycelium or of ally otlier orgaiiisni made its appearance during the nine weeks it was under observation. If it be true theii that the gel-ms of these fungoid and other organ- isnis be usually present in the air and that they develop in a sacelini-inc solution only when tlie latter contains a phosphate it obviously follows 1 that maters whicli are unaffected by this sngar test ought to be in- capable of propagating semer fungus when they are infected.This conclusion was complctely verified on submitting it to tlie test of ex- periment. 10. Harrow decp well mater (see page G8) which had remained per- fectly clear f o r 24 days after aclmixturc with sugar T V ~ S infected with washed sewcr fungus mliicli I collcctccl a t ah. Hope's irrigation farm at Romforcl. After the lapse of fire days during which time it \vas maintained a t a temperature of betmeen GO" and 70" I?. no growth or tulbiclity had occurred. A single drop of solutioii of albumin wag now added ; four days later the water hail become very turbid and nuincroiis fungoicl growths had commeiiced at the bottoiii of tlie bottle.Thesc examined by tlie inicroscope showed mycelium threads not very well developed also leptotliris and abundance of grouped cells with bright nuclei. No vibrios mere observed. Afterwaids the fungoid growth became more abundant but never SO luxuriant as that ob- tained in Experiment No. 9 which surpassed all others. 11. Water from tlie bore-hole in Bushey Meadon-s (see page 68) wliich after the addition of sugar llacl maintained its transparency (luring 24 days was infected as in the last experiment with x-ashed se\ver fungus. No growtli took place ; neither was tlie tmnsparency of the water distuibecl in the subsequent eight weeks during which it mas repeatedly and closely observed. It is thus evident that the presence of germs in a sample of water is insuficieiit in itself to produce Bfr.H e i s c h ' s reaction when sugar is aclded aiitl further that a short (probably iL momentary) contact with air is sufficient to inipregnste any snniple of watcr Kith the necessary germs which develop on thc acldition of sugnr only in the presence of a phosphate. The reaction is in fact an exceedingly deli- cate test for phosphoric acid. It vioiild probably defy the pomers of tlie most espert chemist to detect in two ounces of water the phos- phoric acid introduced by the adclition of a single drop of a dilute solution of albumin xet these atmospheric germs find i t out appro- priate it and by their growth reveal its presence. As a ready means of discorering traccs of phosphoric acid this method will cloubtless often comnieiid itself to chemists ; but I have considerable hopes that IN POTABLE WATER.- 0 73 in a modified and extended form it may be applied to the exploration of both air and water with far more raluable results. If the germ theory of clisease be true niicl it has of late received considerable experimental support it is not improbable that the germ constituciits of the air may undergo such a marked alteration during the prcvalencc of certain forms of epidemic disease as to be recognisablc in the growths which mould ensue in such a fluid as that used in Experiment No. 9 or in a similar one i o xhich some of tlie constituents of our ordinary food were adcled such as albumin milk and juice of flesh. In order t o expose tlicsc fluids with their contained gcrms t o couclitioiis as closely analogous ab possible t o those wli~cli obtain in the alinien- tary canal tlicy Ought to be kept in the dark ancl maintained at bloocl- heeat during incubation.I have made a few experiments in this direction but it is obyious that Iaborious nncl long-continued obser\ ations will be necessary bcfore the ordinary clcvelupmentd phenomena of a healthy atmosphere can be distinguisheJ from those of infected air ancl IT\ i l l tlicreforc only describe one or t v o of the experiments by way of illustrating tlic mode of operating. Tlic process is also obviously equally applicable to the testing of waters intentionally infected by the cvacuntlons of patients suffering from typhoid fever cholera scarlalina ancl other discascs.1%. A sample of water supplied t o London presented three wccks after admixture with sugar and exposure to a tcmpcrature ranging between GO" ancl 70" I?. faint traccs of fungoid growth. It was now placed in a nearly dark chamber a t a temperature of from 78" t o 85" P. After ten hours the dei-clopmcnt of mycelium had gwatly increased but on raising the temperature to 8Y0-99" 3'. for fourtccn hours tlie fungoid threads nearly disappeared. Lcptothris fibres abounded but no vibrios backria or moring orgnnisrns 17-ere seen. 13. Effluent water from B~rking sewage farm was mixed v i t h s n p r and exposed as in Experiment No. 12 to a temperature of from /8 t o 85" P. for ten hours a t the end of whicli time it had bccome slightly turbid and a fungoicl gromth n as observed.The tomperaturo was then increasecl to 98" F. Fme hours later it 1i:d become very turbid and the fungoid gron th had augmented. After tn-enty-two hours' additional exposure to the same temperature the turbidity had con- siderably diminished and the fungoid growth had not progressccl much. The microscope rerenlcd long slender fragile and jointed mycelium threads very different from those which had developed in similar liquids a t more moJerate temperatures. There were also crox-ds of bacteria -vibrios and other moving organisms. Even a t tlie expira- tion of a further period of three d a p during which time a nearly uniform temperature of 98" F. was maintained tlie fungoid growth had not perceptibly increased.FRhNTrLASD ON THE DEVELOPMENT OF FUXGI DISCUSSION. 74 14. Six drops of sewage and tlie usual proportion of sugar were addcd to about 1+ oz. of Grand Junction Compzny's water and the niixture which smelt vcry offensivcly was exposed as before to a temperature varying from 78" to 85" F. At the end of ten hours no pcrccptiblc change hod taken place. The water was now raised t o blood hcat (9s' F.) and maintained a t that temperature until the close of the cxpeyiment. At thc end of five hours it had become turbid from ihe dcvclopment of crowds of bacteria. Even after the lapse of thirty hours morc no vibrios or mycelium were perceptible ; but after tlie expiration of t h e e more days abundant fine long non-branching tubular thrcads with square cells ciiclosed had developed.Some vibrios and cclls with bright nuclei were also seen. k'rom these a i d a number of other similar experiments the conclu- sion mas impressed upon nie that the temperature of the body is favour- able for the production of bacteria vibrios and similar organisms but ui~favourablc for fungoid growths. As already mentioned however these latter esperhnciits mill require to be greatly extended before any trustworthy coiiclusions con be drawn from them. It mould be especi- ally interesting t o make them with water which had been agitated with the air of the fever &c. wards of hospitals. The following are the conclusions to which these experiments have led me :- 1. Potable waters niixed with sewage urine albumin and certain other matters or brought into contact with animal charcoal subse- quently develop fungoid growths and other organisms when small quantities of sugar are dissolved in them and they are exposed to a sunimcr temperature.2. The gcrms of these organisms are present in the atmosphere and evcry water contains them after momentary contact with the air. 3. The dcvelopment of these germs cannot take place without the presence of phosphoric acid or a phosphate or phosphorus in some form of combination. Watcr howerer much contaminated if free from phospliorus does not produce them. A German philosopher has said '' uliiie Y l i o s y l ~ o ~ ~ heiti GetlniiXe." The above experiments warrant the alteration of this dictum to ohrLe Phosplior gar k e i i ~ Leben.P r e s i d e n t It certainly is striking that the absence of phosphorus should cause the observed cleficiency in the fungoid development but was phosphorus wholly absent ? does not the sugar which is purified by means of animal charcoal contain some ? IN POTABLE WATER. 7 5 Prof. F r a n k l a n d The crystallisation of tho sugar probably excludes any appreciable tracc of phosphorus. Mr. H e i s c h In one or two points Dr. F r a n k l a n d ' s obscrvntions are diametrically opposed to my own results. The one is that water cannot be deprived of its germs by filtration through animal charcoal. Now my observations in this respcct ari? not isolated ones but I halve now for about three years been investigating -wcclc after week watcr which passed through charcoal filtcrs arid have never nict with fungoycl developincnt in such water."lie other point of diffcrcncc betwecn Dr. F r a n k l a n d ' s experimcnts and my o ~ n is that whcreas 110 noticed the same kind of cells whether t h y werc originated tlirougli white of egg or through sewage matte;. I obtained in the two C:LSCS very distinct results. The sewago fungus is rcry small pcrfcctly spherical and excessively transparent ; it grows and clccays rather rapidly ; in about six hours after adclition of tho se-rvagc fluid t o tlic sugar solution tlic splierical cclls most,ly in gnpe-likc b;uichcs appcar which after six more hours liavc deve!opcd tlieinselrcs into mycelia and a few hours later are broken up entirely. During the growth of these orgnnisnis the odour of butyric acid was clcarly pcrccptiblc.Now when white of egg was put into a sugar-solution no sniell of butyric acid was emitted during the formation of the cells which were somewhat larger and lcss t.mnspareiit than those in the former case. Dr. Russell The results of my experiaents mostly coincide with those arrived a t by Mi,. Eeisch. I happoned also to submit to the sugar-test a sample of drainage water froin Romforcl Farm aiid ob- tained like Dr. F r a n k l a n d a negntive result,. Mr. B e l l Perhaps the effluent water saniple examined by Dr. Rus- sell was kept for some time. In t'hat case it mould purify itself and give no fungoid growth on addition of sugar. But if the saniplcs of effluent waters are investigated very soon after t h y Ii:~d bccn collected they mill yield fungi Regarding Dr.Franklancl's shtcmcnts I can say that my experiments fully bear out what lie said with rcspcct to the indispensable presence of pliosphates. I can also fully confirm his remarks as to the animal charcoal-it does not take away the germs from the water ; indeed I am inclined to believc h a t these germs lire in the coal. I found burning to be the best mc:ms for purifying the charcoal. ' Dr. Voelcker Nr. B e l l ' s reinark as to thc rapid changc w1iic.h sewage undergoes is quite correct. A jar of sewage left loosely coverecl for some months had lost almost all its ammonia whilst its nitric acid had increased. Since so much doubt is throvm on the efficiency of animal charcoal for purposes of water purification I may mention t h t iron-sponge mould be a,n excellent substitute for chmcoal Gltcrs.This HUNTER ON THE EWECTS O F PRESSURE 7 G spongy iron is obtained by calcining with coal the residues from copper pyrites. Dr. Thudichum thought that the whole fungus theory was nothing better than a vague and wild surmise. l f r . Wariiigton That water which had passed through iron-sponge does not yield fungi on addition of sugar may be due to tlie removal of the phosphoric acid which had been retained by the hydroxide of iron wherewith the sponge is coverecl. As to the experiments with charcoal I wisli t o observe that water filtering through fresh charcoal takes away from it some phosphates but after the filter has been used for a time this will no more be the case.This circumstance may perhaps explain the difference in the observations of Messrs. F r a n k l a n d and Heisch. Dr. D~iprB asked wliether Dr. F r a n k l a n d and Mr. Heisch had boiled tlieir sugar-solutions bcfore mixing them with the waters to be examined? Whenever he (Dr. DuprB) did so he obtained no fungi. Dr. F r a n k l a n d replying [to Dr. DuprB] My sugar-solutions were not boiled but in Experiment No. 9 the water had been previously boiled for a long time and the sugar and all the other substances heated to a much higher degree than that of boiling mater and I obtained more splendid fungi here than in any other case. [To Mr. HBiscli.1 The difference in our obsermtions regarding animal charcoal appears t o be satisfiictorily explained b~ blr. V a r i n g t o n ’ s observations. As to the two fungi from sewage and from white of egg I merely pronounced them to be similar to but not identical with one another. I paid no particular attention to the emission of butyric smcll. [To Mr. Bell.] 1 investigated the effluent water about 24 hours after its collection. (Here Dr. Russell remarked that he had done the same.) [To Dr. Voelcker.] I have also found that sewage is apt to have its ammonia converted into nitric acid. IX.-Ou the Bfecfa of I”1.essw.e on tlie Absorption of Gases by Charcoal. By J O E N HUNTER N.A. F.C.S. F.R.S.E. Professor of Mathematics and Natural Philosophy University of King’s College Windsor Nova Scotia. IN the following memoir I purpose giving the results of a few obser- vations on the effects of pressure on the quantity of a p s absorbed by cocoa-nut charcoal.

ISSN:0368-1769    

DOI:10.1039/JS8712400066

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

HUNTER ON THE EWECTS O F PRESSURE 7 G spongy iron is obtained by calcining with coal the residues from copper pyrites. Dr. Thudichum thought that the whole fungus theory was nothing better than a vague and wild surmise. l f r . Wariiigton That water which had passed through iron-sponge does not yield fungi on addition of sugar may be due to tlie removal of the phosphoric acid which had been retained by the hydroxide of iron wherewith the sponge is coverecl. As to the experiments with charcoal I wisli t o observe that water filtering through fresh charcoal takes away from it some phosphates but after the filter has been used for a time this will no more be the case. This circumstance may perhaps explain the difference in the observations of Messrs. F r a n k l a n d and Heisch.Dr. D~iprB asked wliether Dr. F r a n k l a n d and Mr. Heisch had boiled tlieir sugar-solutions bcfore mixing them with the waters to be examined? Whenever he (Dr. DuprB) did so he obtained no fungi. Dr. F r a n k l a n d replying [to Dr. DuprB] My sugar-solutions were not boiled but in Experiment No. 9 the water had been previously boiled for a long time and the sugar and all the other substances heated to a much higher degree than that of boiling mater and I obtained more splendid fungi here than in any other case. [To Mr. HBiscli.1 The difference in our obsermtions regarding animal charcoal appears t o be satisfiictorily explained b~ blr. V a r i n g t o n ’ s observations. As to the two fungi from sewage and from white of egg I merely pronounced them to be similar to but not identical with one another.I paid no particular attention to the emission of butyric smcll. [To Mr. Bell.] 1 investigated the effluent water about 24 hours after its collection. (Here Dr. Russell remarked that he had done the same.) [To Dr. Voelcker.] I have also found that sewage is apt to have its ammonia converted into nitric acid. IX.-Ou the Bfecfa of I”1.essw.e on tlie Absorption of Gases by Charcoal. By J O E N HUNTER N.A. F.C.S. F.R.S.E. Professor of Mathematics and Natural Philosophy University of King’s College Windsor Nova Scotia. IN the following memoir I purpose giving the results of a few obser- vations on the effects of pressure on the quantity of a p s absorbed by cocoa-nut charcoal.ON THE ABSORPTION UP GASES BY CFLiRCOAL. 77 The form of apparatus employed in ordcr to obtain pressurc in these experiments presents the great advantage of being casily taken to pieces and when very high pressures are not required I hive found it to work admirably. Two strong copper plates (a A) are connected by nieans of t h e e iron rods (T T T) firmly fisteiiecl t o the lower ancl passing tlirough holes in the upper plate \\here they are niade secure by screws aud nuts (B). Each plate contains a groore in n hich is placed a leather maslier covered on the exposecl sur- face with a mixture of white lead and gieLisc. 0 The ground ends of a thick glass cylinder are fitted against the leathers ancl when the plates are screwed together a strong joint i.; formcd capable of resisting a pressure of about fire or six atniosplieres.The pressure is produced by first filling tlie glass cylinder quite full of water T and then introclncing into it an iron screw (S) which works througli leather packing. In performing an experiment a vessel (V) containing mercury is placed on the lower plate. Two tubes are inverted in the mercury ; one partially filled with clry air acts as R manonieter; the othcr con- tains a fragment of cliarcoal and tlie grts under examination. The original volume of the gas is read off befoie introducing the cliarcoal into thc tube ancl after a sufficient time has elapsed the amount of absorption is carcfully determined. The glass c j liuder is tlm~ placed over the tubes and the upper secured to tlic lower plate by means of the screws.The interior of the apparatus is now filled with water and the pressure produced after the screw is measured by observing the volume of the air in the manometer tube. The corresponding diminu- tion in the volume of the gas in the absorption tube is also read off and since me know the original volume of the latter we can easily calculate what it ought to be a t each increase of pressure ancl the difference between the observed and calculated volumes gives the gbsorption. From the necessity of employing a comparatively small quantity of the gas in each experiment rarely more than 5 or G c.c tllc differences corresponding to each increase of pressure are not so regular as I could hare wished ; nevertheless in comparing the results contninccl in the following tables it may be observed first that the amount of absorption increases with the pressure to which tlie gas is exposed ; and secondly the same change of pressure produces about the same amount of increase in the quantity of each gas absorbed.It is worthy of observation that if we compare the relative wciglits VOL. SSIT. 11 HUNTER ON THE EFFECTS OF PRESSURE 78 of the absorbed gases in tlie following tables we find that cocoa-nut charcoal absorbs a greater weight of cyanogeii thnu of either amnionia or carbonic anhydride. In the tables of absorptions :- V = tlie volume of gns absorbed by one volume of cocoa-nut charcoal ai 0" C. a i d the corresponding pressure.P = thc pressurc in millemetres to Trhich the gas is exposed. First Scries. I P. 760 .O 1102 .o 1170.4 1367.2 1479.7 ~ ~~ P. 760 '0 1013.8 1095.9 1149.1 First Scries. V. 170.4 173 .O 176.9 178 '2 179.5 Fourth Series. v. 170 '6 171 .7 173 '0 176 '9 v. 78.2 91 '1 91.7 93.1 P. 760 .O 1009.3 1073.8 1333.6 1.150 5 9G .G Second Series. Third Series. ~~ v. v. lG5.5 l6G .4 173 .O 176.9 v. 172 .? 17s .2 i s 0 .a 193.6 191.8 187.3 190 .o 194 .o 197.5 201 '9 P. 760 .a 110k 3 117s .O 12G9 .2 1369.5 1496 '5 1796.1 2002 '6 2605.5 P. ?GO .O 1490.7 l(;Ss .1 2397 .O 2910 .8 3858 -2 P.850 .7 ?GO .O 1390 2 . 1639 -8 P. 760 .O 829 5 950.2 1021. .D 1112.9 l Z l i . 3 1343 .; 1499 .7 1693 9 1955 9 Third Series. P. - 760 '0 962 .9 10-15 .6 s92.4 1143.7 1262.2 1408 .O 1594.5 67 .i 9s .o l i 0 . 7 171.3 IiCi.0 173 2 180 '8 1s3 5 188 .7 196 .'7 209 '5 Fifth Series. Secoiid Series. v. G 1 . 7 81. .5 86 .O 102 '1 V. 71 '1 77.9 76 ' 9 77 -4 78.4 80 .o 51 '1 82.5 2143.4 88 .G Fonrth Series. P. 80 5 81.5 61 5 88 .0 8G 1 E5 .S First Series. v. 103.5 10G .8 107 7 109.9 112.8 114.5 116'3 129.2 v. ~ 760 .0 935 .G 1035 6 1155 9 150.3 3 130G.h 1778 4 2190.3 v. 106.7 107 .? 103 '5 109 .0 109.9 107.5 107.7 112 0 115 B Second Series. Fifth Series. v. 1 P. 132 4 P. 7G0 .O 1146.8 1510 .F 1886.3 2.103 .1 760 ,0 I llti9.G 1291 2 1628 8 1S73 I. 103.1 113 .0 220-1 ' 7 2678.2 P. 760 '0 GO .a 1051.1 1159 '9 1293 .5 1.163 '0 lGYl.9 19s0 .5 Fourth Serieg. P. 560 .0 1031.3 1101 .2 1182 .5 1 1276.0 1335 '5 1515.4 1865 .S 103 '2 105.1 106.8 108.5 110'3 111.3 112.2 113.3 v. Fifth Series. 1 P. s1 .0 1 1011.G 987 760 .Q 9 53 ' 2 8.5 5 57'3 9.5 5 1 1100 9 1113 8 1625 6 1912 0 I 232h 1 Third Series. P. P. V. 10G .G 111t.1 115 .0 117.1 11s .-J! Sixth Series. V. 102.5 103 4 10 1.7 106 k 113 0 119.3 79 7GO '0 1011.2 1143.3 1315.1 1ss0 '2 760 .0 1212.3 1338.4 19-$2 .5 1493 .4 2286 ' 8

ISSN:0368-1769    

DOI:10.1039/JS8712400076

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

WARINGTOS O N THE SOLUBILITY OF BONE-ASH 80 X-01~ the Solubility qf tlie Pliosphntes of Eone-Ash iii C'trd~oitic T a t e r . By ROBEXT WARISGTOX. IN the year 1866 I brought before the Society some results of an investigatioii into the solubility of tricalcic phosphate under various conditions wliicli might be supposed to occur in soil.* The results described in that paper 7vcre obtained with pure salts artificially pre- ptred. It TWS intended in the nest placc to examine tlie various natural mixtures which form tlie phosphates arnilnblc for agriculture aiid to ascertaiii them solnbility under siinilay conditions The invcsti- p t i o i i of this sccoiid part of tlie subjcct mas conimencccl a t the Ropd Agricultural College during tlie spring of 1867 but n as soon after- wards unnvoiclably relinquishecl.Hnring no prospect of completing the experiments I desire to put on record the results then obtained. Two specimens of hone-ash were tlic pliospliates examined-one n cominercial samplc of unknown history and fhir average qnality the othcr a sample nf pure bone-ash from Roiliamsted liii~dly furnished by Mr. Lawes representing the carcass bones of an entii-e os. These speciniciis of bone-ash Tere analysed ~ ~ i t l i the following results :- Pure Ox Bone-ash. C'omniercid Bono-ash. 1.86 Moisture and volatile matter 6.70 9.69 Siliceous mitter .5s .51 .17 52.46 1.02 Magnesia Pliosphoric acid Oxide of iron Lime 43.37 1.14 33.68 Carbonic acid alldies ancl other sub- stances undet'ermined 4.84 100~00 30.55 4.43 100.00 A preliminary experiment was made with the commercia1 bone-ash.An unknown quantity? T T ~ S treated with mater and carbonic acid passed into the mixture the end of the delivery-tube being so placed that the passage of thc gas kept the bone-ash in suspension. After fivc days the solution was rcmoved and analysed. The results were most unexpected. Ten thousand parts of the solution contained 2.495 P20, a degree of solubility equal to that of gelatinous tricalcic phosphate in carbonic water. A large quantity of magnesia was also * Jonr. Cham. Soc. 1866 rol. iv 11. 296. f In tliia case the bone-ash was mall washed with hot water before the eaperi- ment commenced. This was not doue in the snbsequent experiments.IN CARBONIC VATER. From this first trial it appeared rery probable that x part of tlie phosphoric acid in bone-ash existet1 in a coniparativcly soluble form since it was most milikely that the high degree of solubility just mcn- tioned \.vonld be sustained during snccessive trentnicnts with carbonic water. I n order therefore to asoertain the pmnn~cirt solubility of the phosplixtes of bone-ash 400 grains nf the commercial boiie-ash were placed in a pint bottle and subjectecl t o rc1icatcd trcatrncd mifh water and carbonic acid each solution of bonc-ail1 h i i g removed by dccan- tation and aiinlysed while thc residue Was SllbJCCtell afresh to tllc process of solution tlie intention being to contiinie this mode of pro- ceeding until the amount of pliosphoric acid removed ccascd to vn~y.A similar series of solutions WRS macle witli thc purc bonc-ash ; but i t having been fouiid that the solnbility clccrenscd very slowly in tlie earlier series of experiments only 3C)f) grains of this bonc-ash vcre operated on. I n every case the carbonic water rcrnainecl in coutact fir three or more clays during which gas was pnssed for 1 G to 24 hours. The results obtained are shomn in the following tablus :- SI To td dissolved Total d i s s o l d __ fix 100 1 originally I. Eqieriiiieiits on flw Solubility of Omz~ne~cbiI Boiae-mh. Found in 10,000 parts of each solution. Foulid in 10,000 p u t s of each solution. h-umber of I. 11. solution. I 1 If - - PZOj *.1,010 ,634 coo 1.376 1'188 MgO ,. 2.382 '526 * Determined with uranium t where determinations were wanting an estimate has hcen introdutcd in ciilcn- lating this number. WARISGTOS ON THE SOLUBILITY OF BONE-ASH 52 Between esperimciits T I and TI1 with conimercial bone-ash and between elperimcnts IV and V with pure bone-asli the nuidissolved phosphates were reniovecl fi-om the bobtle aiid recliiced to the finest po wclcr obt niiiablc. 111 thc first series of experiments thcre is a gradual clecliiie in the amount of pliosphoric acid dissolved aiid the figures give no evidence that the miiiiiniim solubility was reaclied eren at the end of the series. The aiiiouiit of pliospiioric acid taken up by the first solution is about three times as great as tlint clissolvecl by the fifteenth treatment with carboiiic water.T'lie real difference betn cen tlie primary and final solubility of tlic bone-aslt pliosplintes \vas probably however far greater tlim this. For siuce i t is showii by the eiperiiiieiits that only n small fi-action of ilic pliospliates possessed a liigli degree of solubility it is clear that to obhin a snturatccl solotion of tliese phosphates it TXLS necess&iry that the qiinnhty of bone-nsli sliunld bear a high relation t o the voliiuie of sul\eiit ~iliiclin fact it c l d not. The magiiesiiuni salts in the bone-ash appmr t o be niuch more soluble tlinii tlie calcium salts as incleecl \I as to be expected from previous rcscarchcs. Tlic laige ainount of magiiesia taken up by tlie hl-st solation is however very reinarliable.Thc last colunin in the table shows tliat tlie carbonic mater had on the whole rciiiovecl phosphoric acid niicl Line in the saiiie proportions as lhey existed in the bone-ash; ancl tlint about two-thirds of the magnesia had becn clissolt ed for one-ninth of tlie pliosplioiic acid ancl liinc. I n tlie series of experiments xi111 pure o s bone-ash it is at oncc evicleiit tliat thc plioapliate \\as of a much more uniform compo- sition thnn the conimeraial bone-ash used in the precediiig trials. The arnouiit of phosphoric ncicl taheii up soon fell to a minimum and remained vcry constaut to the eiicl of tlic erperimcnt though tlie amounts of lime and magnesia remorecl continued to diminish. Taking the iueaii of the last four t r d s as representing the perma- nent solubility of the phosphates of this bone-ash we have a solubility of .Ci75 PJ05 in 10,000 of carboiiic water.+ Or reckoning the plios- plioric acid as tricalcic phosphate for the sake of comparison with other results the solubility is 1 of phosphate of calcium in 6788 of carbonic watcr.Tlie table shoms that the primary snlutbility of tlie phosphates JYas mucli less in the case of the pire bone-ash tiinn in the case of the coin- mercial sample. The diiference is doubtless in part owing t o the smaller quantity of the pare bone-ash operated upon the bulk of fluid * I t will be observed tlist the permanent solubility here obtmned IS qulte near to the last solubility 111 the preceding senes.It seeins probable therefore that tlie ~ I I I I ~ U I U solubility had been almost reecherl in tho first series of experiments. IS CARBONIC WATER. S 3 remaining the same in b3th cases. This fact Iion-cwr can cxpliiin but a sinal1 part of the diffwence ~ h i c l i must) he nixiiily clue t o {#lie more uniform clinrnctcr of the p i r e lione-ash. On coinp:triug ilie analyses of the two 1i:lnc-ashes alrcady quoted the only markcc1 diffcr- ecce wliicli nppenrs is the €ai larger anioaiit o r siliceous innttcr in the commercial sample. It seems likely tliat in t h e process" of cdcinntion the sand had to somc exteut attn8cked tlie phosphate of calcium pro- ducing silicate of calcimu ancl leaving phospliat,es less basic than those constitntfing iiormal bone-ash.If this be thc case tlic grcater primary solubility of the phosphates in the comniercinl bone-as11 was owing to t,he presence of a small portion ofconii?arnti~~lp'nci(l plios~~hnics. The high solubility of the ningncsiimi salts is ci-cx more strikingly shown with tlie pare bone-ash tiinn in thc 1irc~ioiis results. The wliole erect procliiceil by tlic cay!ionic wntcr npon tlie piire bone-ash is's!iovn by the tnb!c t o Iiare co1isistecl in the removal of but t - ~ small qiiantity of the phosphoric ncid a d lime (the latter clissolvecl in somewhat larger proportion t,haii ilia formcr) ~rliile nearly tlic whole of t>lic inagncsin was taken 1112. It is not siipposed th:tt the resnlis of tlissc cletachecl cxperimeiit,~ n,rc of cuucli importance t o the a,~ricultiiral chemist ; it is indced only from a comparison of tlie belizwionr of diffciwit plios~~liatic materials that a117 salnable conclusions are to be expected.Tlic rcsiilts sliim hnnre>-cr unrnistnknblp the vast diiTwcncc wliicli may exist between primary nncl pcrnianeiit soiul)ilit,j- of a complex bocly and point to the 11ecessit~- of operating by the niethod of successive solutions wlieii- ever the perwnnent solnbility is t o be nscertainccl. This inctliod as far as I am :tn-are has been scarcely used and tllc solubilities of natural pliosphntes and other bodies ham been tlioaglit to bc snfIicic*rltIy determined by single or inclependciit cbspcrinicnts. This plan ~vliicli is a11 that is reqiiircd with pure salts is qiiite innclmissiblc n-ii,li coiu- plex bodies ancl must freqiientljr lcnd to very crroneoiis conclusions. Dr. Voelcker observed that the circuiiistance that at first grentcy quantities of phosl1lior;c acid went into solution might be clue to the presence of a11;alis. BIoreoxrer comnicrcial bone-ash is prepared not from pure boues but fI'GIl1 s ~ i C 1 1 ns linre bccn iuisrd with clried blood $c. n-11ic11 of course ~ ~ o n l c l explain the greatcr amount of soluble phosphates. &. Gill remarlceil that in the analyses of commercial bone-ash-so called bone-saw-dust-he h c l mostlF found the albalis in the statc of chlorides. Jlr. Warington confirmed this statemelit.

ISSN:0368-1769    

DOI:10.1039/JS8712400080

出版商:RSC    

年代:1871

数据来源: RSC